TREA

Ethers on esters of 1-triazole-2-substituted ethanols

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Information

  • Patent Grant
  • 4880457
  • Patent Number
    4,880,457
  • Date Filed
    Wednesday, March 16, 1988
    36 years ago
  • Date Issued
    Tuesday, November 14, 1989
    35 years ago
Information
Abstract
A compound of general formula (1) ##STR1## wherein R.sup.1 is C.sub.1-6 alkyl, cyclobutyl, cyclopropyl, cyclopentyl cyclohexyl or phenyl, and R.sup.2 is phenyl or benzyl; the phenyl of R.sup.1 and the phenyl or phenyl moiety of the benzyl of R.sup.2 being optionally substituted with halogen, C.sub.1-6 alkyl, C.sub.1-5 alkoxy, C.sub.1-10 alkoxyalkyl, halo-C.sub.1-4 alkyl, halo-C.sub.1-4 alkoxy, halo-.sub.1-5 alkoxy, halo-C.sub.1-5 alkyl, nitro, phenyl, phenoxy, benzyl, optionally halo-substituted benzyloxy, C.sub.1-2 alkylenedioxy, acetylamino, halo-C.sub.1-2 alkylenedioxy, amino, mono- or di-C.sub.1-4 alkylamino, hydroxy, cyano, morpholino or carboxy or an alkyl ester thereof, and/or the alkyl moiety of the benzyl is optionally substituted with one C.sub.1-4 alkyl; and acid addition salts, ethers, esters and metal complexes thereof. The compounds are useful as fungicides and as plant growth regulating agents.
Description

This invention relates to triazole compounds useful as fungicides and plant growth regulating agents, to a process for preparing them, to fungicidal and plant growth regulating compositions containing them, and to a method of combating fungi, especially fungal infections in plants, and to a method for regulating the growth of plants using them.
The invention provides a triazole compound having the general formula (I): ##STR2## wherein R.sup.1 is C.sub.1-6 alkyl, cyclobutyl, cyclopropyl, cyclopentyl, cyclohexyl or phenyl, and R.sup.2 is phenyl or benzyl; the phenyl of R.sup.1 and the phenyl or phenyl moiety of the benzyl of R.sup.2 being optionally substituted with halogen, C.sub.1-6 alkyl, C.sub.1-5 alkoxy, C.sub.1-10 alkoxyalkyl, halo- C.sub.1-4 alkyl, halo- C.sub.1-4 alkoxy, halo- C.sub.1-5 alkoxy halo- C.sub.1-5 alkyl, nitro, phenyl, phenoxy, benzyl, optionally halo-substituted benzyloxy, C.sub.1-2 alkylenedioxy, acetylamino, halo- C.sub.1-2 alkylenedioxy, amino, mono- or di- C.sub.1-4 alkylamino, hydroxy, cyano, morpholino or carboxy or an alkyl ester thereof, and/or the alkyl moiety of the benzyl is optionally substituted with one C.sub.1-4 alkyl; and acid addition salts/ethers; esters and metal complexes thereof.
The compounds of the invention can contain chiral centres. Such compounds are generally obtained in the form of racemic mixtures. However, these and other mixtures can be separated into individual isomers by methods known in the art.
In a further aspect the invention provides a method as defined above wherein R.sup.1 is C.sub.1-4 alkyl and R.sup.2 is optionally substituted benzyl.
In another aspect the invention provides a method as described above wherein R.sup.1 is optionally substituted phenyl and R.sup.2 is optionally substituted benzyl.
In a yet further aspect the invention provides a method as defined above wherein R.sup.1 and R.sup.2, which may be the same or different, is optionally substituted phenyl.
In a still further aspect the invention provides a method as defined above wherein R.sup.1 is C.sub.1-4 aklyl and R.sup.2 is optionally substituted phenyl.
When R.sup.1 is alkyl it can be a straight or branched chain group having 1 to 6, e.g. 1 to 4 carbon atoms; examples are methyl, ethyl, propyl (n- or iso-propyl), butyl (n-, sec-, iso- or t-butyl), pentyl (e.g. n-pentyl) and hexyl (e.g. n-hexyl). It is preferably butyl, especially t-butyl.
Examples of suitable substituents for the phenyl and for the phenyl moiety of the benzyl are halogen (e.g. fluorine, chlorine or bromine), C.sub.1-5 alkyl [e.g. methyl, ethyl, propyl (n- or iso-propyl) and butyl (n-, sec-, iso-or t-butyl], C.sub.1-4 alkoxy (e.g. methoxy and ethoxy), halo- C.sub.1-4 alkyl (e.g. trifluoromethyl or 1, 1, 2, 2-tetrafluoroethyl), halo- C.sub.1-4 alkoxy (e.g. trifluoromethoxy or 1, 1, 2, 2-tetrafluoroethoxy), nitro, phenyl, phenoxy, benzyl, benzyloxy (optionally ring substituted with halogen), alkylenedioxy, haloalkylenedioxy (e.g. difluoromethylenedioxy), amino, mono- or di- C.sub.1-4 alkylamino (e.g. dimethylamino), hydroxy, morpholino and carboxy (and alkyl esters thereof). The alkyl moiety of the benzyl can be substituted with for example one alkyl (e.g. methyl or ethyl). Suitably the phenyl and benzyl are unsubstituted or substituted with 1, 2 or 3 ring substitutents as defined above. Preferably the benzyl and phenyl have a single ring substituent in the 2- or 4- position. Examples of these groups are phenyl, benzyl, -methylbenzyl, 2-, 3- or 4-chlorophenyl, 2,4- or 2,6-dichlorophenyl, 2-, 3- or 4-fluorophenyl, 2,4- or 2,6-difluorophenyl, 2-, 3- or 4-bromophenyl, 2-chloro-4-fluorophenyl, 2-fluoro-4-chlorophenyl, 2-chloro-6-fluorophenyl, 2-, 3- or 4-methoxyphenyl, 2, 4-dimethoxyphenyl, 2-, 3- or 4-ethoxyphenyl, 2-, 3- or 4-nitrophenyl, 2-chloro-4-nitrophenyl, 2-chloro-5-nitrophenyl, 2-, 3- or 4-methylphenyl, 2,4-dimethylphenyl, 2-, 3- or 4-t-butylphenyl, 2-, 3- or 4-trifluoromethylphenyl, 2-, 3- or 4-trifluoromethoxyphenyl, 2-, 3- or 4-(1,1,2,2-tetrafluoroethyl)phenyl, 2,3-(difluoromethylenedioxy phenyl), 2-fluoro-4-methoxyphenyl, 2-methoxy- 4-fluorophenyl, 2-methoxy-4-chlorophenyl, 2-methoxy-4-fluorophenyl, 2-, 3- or 4-phenoxyphenyl, 2-, 3-or 4-phenylphenyl (2-, 3- or 4-bisphenylyl), 2-, 3- or 4-benzylphenyl, 2-, 3- or 4-benzyloxyphenyl, 2-, 3- or 4-(4-chloro-or 4-fluorobenzyloxy)phenyl, 2-, 3- or 4-aminophenyl, 2-, 3- or 4-(N,N-dimethylamino)phenyl, 2-, 3- or 4-hydroxyphenyl, 2-, 3- or 4-carboxyphenyl, 2-, 3- or 4-(methoxycarbonyl)phenyl, 2-, 3- or 4-morpholinophenyl and the corresponding ring substituted benzyl and .alpha.-methyl benzyl groups.
In a further aspect, therefore the invention provides compounds as defined above wherein R.sup.1 and R.sup.2 are both halophenyl and preferably one wherein R.sup.1 and R.sup.2, which may be the same or different, are each chlorophenyl or fluorophenyl.
Furthermore in another aspect the invention provides compounds as defined above wherein at least one phenyl ring also bears one or more alkoxy groups, and, for example R.sup.1 may be 2-chloro-4-methoxyphenyl when R.sup.2 is 2-chloro-, 2-fluoro, 4-chloro- or 4-fluoro-phenyl.
Preferred compounds according to the invention are: 1-(1,2,4-triazol-1-yl)-2-(4-fluorophenyl)2-(4-chlorophenyl)ethan-2-ol; 1-(1,2,4-triazol-1-yl)-2-(2-fluorophenyl)-2-(4-fluorophenyl)ethan-2-ol; 1-(1,2,4-triazol-1-yl)-2-(4-fluorophenyl)-2-(2,4-dichlorophenyl)ethan-2-ol; 1-(1,2,4-triazol-1-yl)-2,2-di(4-fluorophenyl)ethan-2-ol; 1-(1,2,4-triazol-1-yl)-2-(4-chlorophenyl)-2-(2-chlorophenyl)ethan-2-ol; 1-(1,2,4-triazol-1-yl)-2(4-fluorophenyl)-2-(2-chlorophenyl)ethan-1-ol; 2,2-dimethyl-3-(2-methoxybenzyl)-4-(1,2,4-triazol-1-yl)-butan-3-ol; 1-(1,2,4-triazol-1-yl)-2-(2-chloro-4-methoxyphenyl)-2-(4-fluorophenyl)ethan-2-ol; 1-(1,2,4-triazol-1-yl)-2-(4-chlorophenyl)-3,3-dimethyl-butan-2-ol; 1-(1,2,4-triazol-1-yl)-bis-2-(4-fluorophenyl)-2-methoxy-ethane; 1-(1,2,4-triazol-1-yl)-2-(4-fluorophenyl2-(2-fluoro-4-methyl-phenyl)ethan-2-ol; 1-(1,2,4-triazol-1-yl)2-(4-fluorophenyl)-2 -(2-chloro-4-methyl-phenyl)ethan-2-ol;
The invention includes ethers and esters of compounds defined above. Preferred ethers are C.sub.1-6 alkyl ethers, C.sub.3-4 alkenyl ethers, optionally-substituted benzyl ethers, for example, methyl, ethyl, propyl, butyl, amyl, hexyl, allyl, benzyl and chlorobenzyl ethers. Thus, in the case of the benzyl ethers, the benzyl may be unsubstituted or substituted with chlorine. These may be straight or branched chain radicals or groups. Particularly preferred are the methyl ethers, especially the methyl ethers of the preferred, and specific compounds, set out herein. As regards esters these may be alkanyoyl, alkenoyl, alkynoyl or aroyl esters, for example, acetyl, acryloyl, crotonoyl, ethanoyl, propionoyl, butyryl, benzoyl, halo- or nitro- substituted benzoyl esters and, again, where appropriate these may be straight or branched chain radicals or groups.
The salts can be salts with inorganic or organic acids e.g. hydrochloric, nitric, sulphuric, acetic, p-toluenesulphonic or oxalic acid.
Suitably the metal complex is one including, as the metal, copper, zinc, manganese or iron. It preferably has the general formula: ##STR3## where Y, R.sup.1 and R.sup.2 are as defined above, M is a metal, A is an anion (e.g. a chloride, bromide, iodide, nitrate, sulphate or phosphate anion), n is 2 or 4, y is 0 or an integer of 1 to 12, and m is an integer consistent with valency.
Examples of the compounds of the invention are shown in Table I.
TABLE I__________________________________________________________________________COMPOUND NO R.sup.1 R.sup.2 MELTING POINT__________________________________________________________________________ (.degree.C.)1 C.sub.6 H.sub.5 C.sub.6 H.sub.5 CH.sub.2 124-1252 C.sub.6 H.sub.5 p-ClC.sub.6 H.sub.4 CH.sub.2 144-1453 C.sub.6 H.sub.5 p-FC.sub.6 H.sub.4 CH.sub.2 116-1184 p-ClC.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4 CH.sub.2 80-835 p-Cl-C.sub.6 H.sub.4 C.sub.6 H.sub.5 CH.sub.2 109-1116 p-FC.sub.6 H.sub.4 C.sub.6 H.sub.5 CH.sub.2 141-1427* C.sub.6 H.sub.5 2,4-diClC.sub.6 H.sub.3 CH.sub.2 104-1068 p-FC.sub.6 H.sub.4 p-FC.sub.6 H.sub.4 CH.sub.2 154-1569 p-FC.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4 CH.sub.2 168-17010 t-Bu C.sub.6 H.sub.5 CH.sub.2 110-11111 t-Bu p-ClC.sub.6 H.sub.4 CH.sub.2 86-8712 t-Bu p-FC.sub.6 H.sub.4 CH.sub.2 146-14813 C.sub.6 H.sub.5 o-FC.sub.6 H.sub.4 CH.sub.2 133-13414 p-ClC.sub.6 H.sub.4 o-FC.sub.6 H.sub.4 CH.sub.2 95-9615 C.sub.6 H.sub.5 o-ClC.sub.6 H.sub.4 CH.sub.2 69-7116 p-MeOC.sub.6 H.sub.4 C.sub.6 H.sub.5 CH.sub.2 100-10317 C.sub.6 H.sub.5 C.sub.6 H.sub.5 128-12918.sup.+ p-FC.sub.6 H.sub.4 p-FC.sub.6 H.sub.4 CH.sub.2 161-16319 C.sub.6 H.sub.5 2,4-diClC.sub.6 H.sub.3 CH.sub.2 104-106 *Includes 1 mole of C.sub.2 H.sub.5 OH .sup.+ This compound is a different crystalline form of compound no. 8
20 t-Bu o-ClC.sub.6 H.sub.4 CH.sub.2 74-7521 t-Bu O-FC.sub.6 H.sub.4 CH.sub.2 96-9822 t-Bu m-ClC.sub.6 H.sub.4 CH.sub.2 88-8923 t-Bu m-CF.sub.3C.sub.6 H.sub.4 CH.sub.2 106-10724 C.sub.6 H.sub.5 p-t-Bu C.sub.6 H.sub.4 CH.sub.2 80-8325 p-ClC.sub.6 H.sub.4 C.sub.6 H.sub.5 83-8526 p-ClC.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4 147-14827 p-ClC.sub.6 H.sub.4 p-FC.sub.6 H.sub.4 154-15528 2,4-diClC.sub.6 H.sub.3 C.sub.6 H.sub.5 191-19429 p-FC.sub.6 H.sub.4 p-FC.sub.6 H.sub.4 170-17130 p-FC.sub.6 H.sub.4 C.sub.6 H.sub.5 139-14031 i-Bu C.sub.6 H.sub.5 94-9532 n-Bu p-ClC.sub.6 H.sub.5 95-9733 t-Bu 2-Cl6-FC.sub.6 H.sub.3 CH.sub.234 t-Bu 2-Cl4-FC.sub.6 H.sub.3 CH.sub.2 9535 t-Bu 2-F4-ClC.sub.6 H.sub.3 CH.sub.2 104-10636 t-Bu 2,4-diClC.sub.6 H.sub.3 CH.sub.237 t-Bu 2,6-diClC.sub.6 H.sub.3 CH.sub.238 t-Bu 2,6-diFC.sub.6 H.sub.3 CH.sub.239 p-OCF.sub.2 HC.sub.6 H.sub.4 C.sub.6 H.sub.5 glass40 C.sub.6 H.sub.5 p-t-BuC.sub.6 H.sub.4 131-135.degree.41 C.sub.6 H.sub.5 o-ClC.sub.6 H.sub.4 142-143.degree.42 C.sub.6 H.sub.5 o-FC.sub.6 H.sub.4 126-128.degree.43 p-ClC.sub.6 H.sub.4 o-ClC.sub.6 H.sub.4 137-138.degree.44 p-ClC.sub.6 H.sub.4 o-FC.sub.6 H.sub.4 144-145.degree.45 p-FC.sub.6 H.sub.4 o-ClC.sub.6 H.sub.4 115-116.degree.46 p-FC.sub.6 H.sub.4 o-FC.sub.6 H.sub.4 120-123.degree.47 C.sub.6 H.sub.5 o-C.sub.6 H.sub.5 OC.sub.6 H.sub.448 p-ClC.sub.6 H.sub.4 o-C.sub.6 H.sub.5 OC.sub.6 H.sub.449 C.sub.6 H.sub.5 o-MeC.sub.6 H.sub.4 161-162.degree.50 p-ClC.sub.6 H.sub.4 o-MeC.sub.6 H.sub.4 157-158.degree.51 2,4-diClC.sub.6 H.sub.3 p-FC.sub.6 H.sub.4 137-138.degree.52 o-ClC.sub.6 H.sub.4 p-MeOC.sub.6 H.sub.4 184-185.degree.53 2,4-diClC.sub.6 H.sub.3 p-ClC.sub.6 H.sub.4 174-175.degree.54 2,4-diClC.sub.6 H.sub.3 o-ClC.sub.6 H.sub.4 149-151.degree.55 2,4-diClC.sub.6 H.sub.3 o-FC.sub.6 H.sub.4 146-147.degree.56 p-C.sub.6 H.sub.5 CH.sub.2 OC.sub.6 H.sub.4 C.sub.6 H.sub.5 134-136.degree.57 p-(p-ClC.sub.6 H.sub.4 CH.sub.2 O) C.sub.6 H.sub.5 98-100.degree. C.sub.6 H.sub.458 m-ClC.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4 139-142.degree.59 p-(p-FC.sub.6 H.sub.4 CH.sub.2 O) C.sub.6 H.sub.5 105-107.degree. C.sub.6 H.sub.460 m-ClC.sub.6 H.sub.4 p-FC.sub.6 H.sub.4 190-193.degree.61 m-ClC.sub.6 H.sub.4 p-MeOC.sub.6 H.sub.4 58-60.degree.62 2,4-diClC.sub.6 H.sub.3 m-ClC.sub.6 H.sub.4 139-142.degree.63 o-MeC.sub.6 H.sub.4 p-FC.sub.6 H.sub.4 200-201.degree.64 p-FC.sub.6 H.sub.4 p-CO.sub.2 CH.sub.3C.sub.6 H.sub.4 164-166 (HCl Salt)65 p-OC.sub.2 H.sub.5C.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4 126-127.degree.66 p-OCF.sub.2 HC.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4 glass67 p-OCF.sub.2 HC.sub.6 H.sub.4 o-ClC.sub.6 H.sub.4 glass68 o-BrC.sub.6 H.sub.4 C.sub.6 H.sub.569 o-BrC.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4 151-152.degree.70 o-BrC.sub.6 H.sub.4 p-FC.sub.6 H.sub.4 109-111.degree.71 p-NO.sub.2C.sub.6 H.sub.4 C.sub.6 H.sub.5 164-166.degree.72 2-Cl5-NO.sub.2C.sub.6 H.sub.3 C.sub.6 H.sub.5 206-208.degree.73 2-Cl4-NO.sub.2C.sub.6 H.sub.3 p-ClC.sub.6 H.sub.474 o-NH.sub.2C.sub.6 H.sub.4 C.sub.6 H.sub.575 p-MeC.sub.6 H.sub.4 C.sub.6 H.sub.5 125-127.degree.76 o-CO.sub.2 HC.sub.6 H.sub.4 p-FC.sub.6 H.sub. 477 o-CO.sub.2 MeC.sub.6 H.sub.4 p-FC.sub.6 H.sub.478 o-CO.sub.2 HC.sub.6 H.sub.4 C.sub.6 H.sub.579 o-CO.sub.2 MeC.sub.6 H.sub.4 C.sub.6 H.sub.580 o-OHC.sub.6 H.sub.4 C.sub.6 H.sub.581 o-MeOC.sub.6 H.sub.4 C.sub.6 H.sub.5 113-116.degree.82 o-MeOC.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4 129-131.degree.83 o-MeOC.sub.6 H.sub.4 p-FC.sub.6 H.sub.4 133-135.degree.84 p-OHC.sub.6 H.sub.4 C.sub.6 H.sub.585 p-BrC.sub.6 H.sub.4 C.sub.6 H.sub.5 104-105.degree.86 p-BrC.sub.6 H.sub.4 p-BrC.sub.6 H.sub.4 159-160.degree.87 p-BrC.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4 138-139.degree.88 p-(CH.sub.3).sub.2 NC.sub.6 H.sub.4 C.sub.6 H.sub.589 o-MeC.sub.6 H.sub.4 p-MeC.sub.6 H.sub.4 117-120.degree.90 o-ClC.sub.6 H.sub. 4 p-MeC.sub.6 H.sub.4 169-170.degree.91 o-FC.sub.6 H.sub.4 p-MeC.sub.6 H.sub.4 156-158.degree.92 o-BrC.sub.6 H.sub.4 p-MeC.sub.6 H.sub.493 o-NH.sub.2C.sub.6 H.sub.4 p-ClC.sub.6 H.sub.494 o-CO.sub.2 HC.sub.6 H.sub.4 p-MeC.sub.6 H.sub.495 o-CO.sub.2 MeC.sub.6 H.sub.4 p-MeC.sub.6 H.sub.496 p-MOC.sub.6 H.sub.4 C.sub.6 H.sub.597 p-FC.sub.6 H.sub.4 p-NO.sub.2C.sub.6 H.sub.4 145-148.degree.98 o-CO.sub.2 HC.sub.6 H.sub.4 p-BrC.sub.6 H.sub.499 o-CO.sub.2 MeC.sub.6 H.sub.4 p-BrC.sub.6 H.sub.4100 o-CO.sub.2 HC.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4101 o-CO.sub.2 MeC.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4102 p-MeC.sub.6 H.sub.4 p-MeC.sub.6 H.sub.4 153-154.degree.103 2,4-diMeC.sub.6 H.sub.3 C.sub.6 H.sub.5 148-9.degree.104 m-NO.sub.2C.sub.6 H.sub.4 C.sub.6 H.sub.5 212-215.degree. (HCl salt)105 o-ClC.sub.6 H.sub.4 o-ClC.sub.6 H.sub.4 164-166.degree.106 o-CF.sub.3C.sub.6 H.sub.4 C.sub.6 H.sub.5107.sup.+ m-CF.sub.3C.sub.6 H.sub.4 C.sub.6 H.sub.5 115-117.degree.108 p-CF.sub.3C.sub.6 H.sub.4 C.sub.6 H.sub.5 207-210.degree. (HCl salt)109 m-CF.sub.3C.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4 104-106.degree.110 p-OCF.sub.3C.sub.6 H.sub.4 C.sub.6 H.sub.5 glass111 p-OCF.sub.3C.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4 107-108.degree.112 p-OCF.sub.3C.sub.6 H.sub.4 o-ClC.sub.6 H.sub.4 99-100.degree.113 p-OCF.sub.3C.sub.6 H.sub.4 p-OCF.sub.3C.sub.6 H.sub.4114 m-OCF.sub.3C.sub.6 H.sub.4 C.sub.6 H.sub.5115 m-OCF.sub.3C.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4116 m-OCF.sub.3C.sub.6 H.sub. 4 p-BrC.sub.6 H.sub.4117 o-OCF.sub.2 CHF.sub.2C.sub.6 H.sub.4 C.sub.6 H.sub.5 188-189.degree.118 o-OCF.sub.2 CHF.sub.2C.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4 94-95.degree.119 m-OCF.sub.2 CHF.sub.2C.sub.6 H.sub.4 C.sub.6 H.sub.5120 m-OCF.sub.2 CHF.sub.2C.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4121 p-OCF.sub.2 CHF.sub.2C.sub.6 H.sub.4 C.sub.6 H.sub.5 glass122* p-OCF.sub.2 CHF.sub.2C.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4 glass123 p-OCF.sub.2 CHF.sub.2C.sub.6 H.sub.4 p-OCF.sub.2 CHF.sub.2C.sub.6 H.sub.4 glass124 3,4-ZC.sub.6 H.sub.4 C.sub.6 H.sub.5 .sup.+ melting point of HCl salt of this compound is *melting point of the 1:1 complex of this compound with isopropyl alcohol is 74.5-77.5.degree..125 3,4-ZC.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4 Glass126 3,4-ZC.sub.6 H.sub.4 o-ClC.sub. 6 H.sub.4127 3,4-ZC.sub.6 H.sub.4 p-FC.sub.6 H.sub.4128 t-Bu o-BrC.sub.6 H.sub.4 CH.sub.2 111-115.degree.129 t-Bu 2,4-diFC.sub.6 H.sub.3 CH.sub.2 140.degree.130 t-Bu o-MeOC.sub.6 H.sub.4 CH.sub.2 113-116.degree.131 Me C.sub.6 H.sub.5 Oil132 Me p-ClC.sub.6 H.sub.4 88-90.degree.133 Me 2,4-diClC.sub.6 H.sub.3 77-81.degree.134 Me p-FC.sub.6 H.sub.4135 Me o-ClC.sub.6 H.sub.4136 Me o-FC.sub.6 H.sub.4137 Me o-MeC.sub.6 H.sub.4138 Me 2,4-diMeC.sub.6 H.sub.3139 Et C.sub.6 H.sub.5 96-97.degree.140 Et p-ClC.sub.6 H.sub.4 105-106.degree.141 Et 2,4-diClC.sub.6 H.sub.3142 Et p-FC.sub.6 H.sub.4 94.degree.143 Et o-ClC.sub.6 H.sub.4144 Et o-FC.sub.6 H.sub.4145 Me o-MeC.sub.6 H.sub.4146 Me 2,4-diMeC.sub.6 H.sub.3147 n-Pr C.sub.6 H.sub.5 77-79.degree.148 n-Pr p-ClC.sub.6 H.sub.4149 n-Pr p-FC.sub.6 H.sub.4150 n-Pr 2,4-diClC.sub.6 H.sub.3151 n-Pr o-ClC.sub.6 H.sub.4152 n-Pr o-FC.sub.6 H.sub.4153 n-Pr o-MeC.sub.6 H.sub.4154 n-Pr 2,4-diMeC.sub.6 H.sub.3155 n-Pr p-MeOC.sub.6 H.sub.4156 n-Pr o-MeOC.sub.6 H.sub.4157 i-Pr C.sub.6 H.sub.5158 i-Pr p-ClC.sub.6 H.sub.4159 i-Pr p-FC.sub.6 H.sub.4160 i-Pr 2,4-diClC.sub.6 H.sub.3161 i-Pr o-ClC.sub.6 H.sub.4162 i-Pr o-FC.sub.6 H.sub.4163 i-Pr o-MeC.sub.6 H.sub.4164 i-Pr 2,4-diMeC.sub.6 H.sub.3165 i-Pr o-MeOC.sub.6 H.sub.4166 i-Pr p-MeOC.sub.6 H.sub.4167 C.sub.3 H.sub.5 C.sub.6 H.sub.5 91-92.degree.168 C.sub.3 H.sub.5 p-ClC.sub.6 H.sub.4 Oil169 C.sub.3 H.sub.5 p-FC.sub.6 H.sub.4170 C.sub.3 H.sub. 5 2,4-diClC.sub.6 H.sub.3171 C.sub.3 H.sub.5 o-ClC.sub.6 H.sub.4172 C.sub.3 H.sub.5 o-FC.sub.6 H.sub.4173 C.sub.3 H.sub.5 o-MeC.sub.6 H.sub.4174 C.sub.3 H.sub.5 2,4-diMeC.sub.6 H.sub.3175 C.sub.3 H.sub.5 o-MeOC.sub.6 H.sub.4176 C.sub.3 H.sub.5 p-MeOC.sub.6 H.sub.4 101-2.degree.177 n-Bu C.sub.6 H.sub.5 62-63.degree.178 n-Bu p-FC.sub.6 H.sub.4 93-95.degree.179 n-Bu 2,4-diClC.sub.6 H.sub.3 106-108.degree.180 n-Bu o-ClC.sub.6 H.sub.4181 n-Bu o-FC.sub.6 H.sub.4182 n-Bu o-Me-C.sub.6 H.sub.4183 n-Bu 2,4-diMeC.sub.6 H.sub.3184 n-Bu o-MeOC.sub.6 H.sub.4185 n-Bu p-MeOC.sub.6 H.sub.4186 i-Bu p-ClC.sub.6 H.sub.4187 i-Bu p-FC.sub.6 H.sub.4188 i-Bu 2,4-diClC.sub.6 H.sub.3189 i-Bu o-ClC.sub.6 H.sub.4190 i-Bu o-FC.sub.6 H.sub. 4191 i-Bu o-MeC.sub.6 H.sub.4192 i-Bu 2,4-diMeC.sub.6 H.sub.3193 i-Bu p-MeOC.sub.6 H.sub.4194 i-Bu o-MeOC.sub.6 H.sub.4195 t-Bu C.sub.6 H.sub.5 75.degree.196 t-Bu p-ClC.sub.6 H.sub.4 70-73.degree.197 t-Bu 2,4-diClC.sub.6 H.sub.3198 t-Bu p-FC.sub.6 H.sub.4 92-3.degree.199 t-Bu o-ClC.sub.6 H.sub.4200 t-Bu o-FC.sub.6 H.sub.4201 t-Bu o-MeC.sub.6 H.sub.4202 t-Bu 2,4-diMeC.sub.6 H.sub.3203 t-Bu o-MeOC.sub.6 H.sub.4204 t-Bu p-MeOC.sub.6 H.sub.4 48.degree.205 n-Pe C.sub.6 H.sub.5206 n-Pe p-ClC.sub.6 H.sub.4207 n-Pe 2,4-diClC.sub.6 H.sub.3208 n-Pe p-FC.sub.6 H.sub.4209 n-Pe o-ClC.sub.6 H.sub.4210 n-Pe o-FC.sub.6 H.sub.4211 n-Pe o-MeC.sub.6 H.sub.4212 n-Pe 2,4-diMeC.sub.6 H.sub.3213 n-Pe o-MeOC.sub.6 H.sub.4214 n-Pe p-MeOC.sub.6 H.sub. 4215 C.sub.5 H.sub.9 C.sub.6 H.sub.5216 C.sub.5 H.sub.9 p-ClC.sub.6 H.sub.4217 C.sub.5 H.sub.9 2,4-diClC.sub.6 H.sub.3218 C.sub.5 H.sub.9 p-FC.sub.6 H.sub.4219 C.sub.5 H.sub.9 o-ClC.sub.6 H.sub.4220 C.sub.5 H.sub.9 o-FC.sub.6 H.sub.4221 C.sub.5 H.sub.9 o-MeC.sub.6 H.sub.4222 C.sub.5 H.sub.9 p-MeC.sub.6 H.sub.4223 C.sub.5 H.sub.9 o-MeOC.sub.6 H.sub.4224 C.sub.5 H.sub.9 p-MeOC.sub.6 H.sub.4225 n-He C.sub.6 H.sub.5226 n-He p-ClC.sub.6 H.sub.4227 n-He 2,4-diClC.sub.6 H.sub.3228 n-He p-FC.sub.6 H.sub.4 97-99.degree.229 n-He o-ClC.sub.6 H.sub.4230 n-He o-FC.sub.6 H.sub.4231 n-He o-MeC.sub.6 H.sub.4232 n-He 2,4-diMeC.sub.6 H.sub.3233 n-He o-MeOC.sub.6 H.sub.4234 n-He p-MeOC.sub.6 H.sub.4235 C.sub.6 H.sub.11 C.sub.6 H.sub.5 110-111.degree.236 C.sub.6 H.sub.11 p-ClC.sub.6 H.sub.4 45.degree.237 C.sub.6 H.sub.11 2,4-diClC.sub.6 H.sub.4238 C.sub.6 H.sub.11 p-FC.sub.6 H.sub.4239 C.sub.6 H.sub.11 o-ClC.sub.6 H.sub.4240 C.sub.6 H.sub.11 o-FC.sub.6 H.sub.4241 C.sub.6 H.sub.11 o-MeC.sub.6 H.sub.4242 C.sub.6 H.sub.11 2,4-diMeC.sub.6 H.sub.3243 C.sub.6 H.sub.11 o-MeOC.sub.6 H.sub.4244 C.sub.6 H.sub.11 p-MeOC.sub.6 H.sub.4 92-4.degree.245 t-Bu 2-F4-MeOC.sub.6 H.sub.3 CH.sub.2246 t-Bu 2-MeO4-FC.sub.6 H.sub.3 CH.sub.2247 t-Bu 2-MeO4-ClC.sub.6 H.sub.3 CH.sub.2248 t-Bu p-MeOC.sub.6 H.sub.4 CH.sub.2 130-131.degree.249 t-Bu p-CF.sub.3C.sub.6 H.sub.4 CH.sub.2250 3-NO.sub.2 4-ClC.sub.6 H.sub.3 C.sub.6 H.sub.5 139-141251 m-ClC.sub.6 H.sub.4 C.sub.6 H.sub.5 108-110252 m-FC.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4 55-59253 m-FC.sub.6 H.sub.4 p-FC.sub.6 H.sub.4 116-118254 p-OCH.sub.3 C.sub.6 H.sub.4 C.sub.6 H.sub.5 88-89255 p-OC.sub.6 H.sub.5C.sub.6 H.sub.4 C.sub.6 H.sub.5 103-105256 o-OCH.sub.3C.sub.6 H.sub.4 p-OCH.sub.3C.sub.6 H.sub.4 133-134257 o-FC.sub.6 H.sub.4 p-OCH.sub.3C.sub.6 H.sub.4 144-145258 p-NO.sub.2C.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4 157-158259 p-OCH.sub.3C.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4 105-106260 p-OC.sub.6 H.sub.5C.sub.6 H.sub.4 o-ClC.sub.6 H.sub.4 100-102261 p-OC.sub.6 H.sub.5C.sub.6 H.sub.4 o-FC.sub.6 H.sub.4 132-133262 o,p-diClC.sub.6 H.sub.3 p-OCH.sub.3C.sub.6 H.sub.4 178-180263 p-OCH.sub.3C.sub.6 H.sub.4 p-FC.sub.6 H.sub.4 124-125264 p-OCF.sub.2 CHF.sub.2C.sub.6 H.sub.4 o,pdiClC.sub.6 H.sub.3 125-126265 p-CO.sub.2 MeC.sub.6 H.sub.4 C.sub.6 H.sub.5 70-72266 p-CNC.sub.6 H.sub.4 C.sub.6 H.sub.5 82-85267 p-CH.sub.3C.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4 134-135268 p-CH.sub.3C.sub.6 H.sub.4 p-FC.sub.6 H.sub.4 124-125269 o-OCH.sub.3C.sub.6 H.sub.4 2,4-diClC.sub.6 H.sub.3 152-153270 p-OC.sub.6 H.sub.5C.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4 gum HCl salt m.p. 177-178271 p-OC.sub.6 H.sub.5C.sub.6 H.sub.4 p-FC.sub.6 H.sub.4 138-140 HCl salt m.p. 171-173272 p-OCH(CH.sub.3).sub.2C.sub.6 H.sub.4 p-ClC.sub.6 H.sub.4 151-153273 n-Bu p-CH.sub.3C.sub.6 H.sub.4 80-81274 n-He p-CH.sub.3C.sub.6 H.sub.4 76-78275 4-OCF.sub.3C.sub.6 H.sub.4 2-FC.sub.6 H.sub.4 glass276 " 4-FC.sub.6 H.sub.4 132-133277 " 2-OCH.sub.3C.sub.6 H.sub.4 115-116278 2-OCF.sub.2 HC.sub.6 H.sub.4 2-ClC.sub.6 H.sub.4 114-115279 2-OCF.sub.2 CF.sub.2 HC.sub.6 H.sub.4 4-FC.sub.6 H.sub.4 115-116280 4-OCF.sub.2 CF.sub.2 HC.sub.6 H.sub.4 " 125-126281 " 2-FC.sub.6 H.sub.4 110-111282 ##STR4## 4-ClC.sub.6 H.sub.4 129-130283 2,4-diClC.sub.6 H.sub.3 -n-C.sub.3 H.sub.7 (CH.sub.3)CH.CH.sub.2 ##STR5##284 2-ClC.sub.6 H.sub.4 4-OC.sub.2 H.sub.5C.sub.6 H.sub.4 94-96285 2,4-diClC.sub.6 H.sub.3 4-OC.sub.2 H.sub.5C.sub.6 H.sub.4 159-161286 4-ClC.sub.6 H.sub.4 4-NH.sub.2C.sub.6 H.sub.4 56287 4-Cl C.sub.6 H.sub.4 4-CH.sub.3 CONHC.sub.6 H.sub.4 70-75288 4-ClC.sub.6 H.sub.4 4-CNC.sub.6 H.sub.4 160289 4-FC.sub.6 H.sub.4 4-CNC.sub.6 H.sub.4 139-140290 4-CH.sub.3C.sub.6 H.sub.4 2,4-diClC.sub.6 H.sub.3 183291 2-ClC.sub.6 H.sub.4 2-OCH.sub.3C.sub.6 H.sub.4 148-150292 4-CNC.sub.6 H.sub.4 2,4-diClC.sub.6 H.sub.3 182-184293 2-F4-OCH.sub.3C.sub.6 H.sub.3 4-FC.sub.6 H.sub.4 161-162294 2-Cl4-OCH.sub.3C.sub.6 H.sub.3 4-FC.sub.6 H.sub.4 138-140295 2-Cl4-OCH.sub.3C.sub.6 H.sub.3 4-ClC.sub.6 H.sub.4 176-177296 2-F4-OCH.sub.3C.sub.6 H.sub.3 2-ClC.sub.6 H.sub.4 170-172297 2-F4-OCH.sub.3C.sub.6 H.sub.3 4-ClC.sub.6 H.sub.4 134-136298 2-Cl4-CH.sub.3C.sub.6 H.sub.3 4-FC.sub.6 H.sub.4 158299 2-CH.sub.34-ClC.sub.6 H.sub.3 4-FC.sub.6 H.sub.4 65-67300 2-F4-CH.sub.3C.sub.6 H.sub.3 4-FC.sub.6 H.sub.4 --301 C.sub.4 H.sub.7 C.sub.6 H.sub.5 Oil302 4-NO.sub.2C.sub.6 H.sub.4 4-NO.sub.2C.sub.6 H.sub.4303 4-NH.sub.2C.sub.6 H.sub.4 4-NH.sub.2C.sub.6 H.sub.4304 .sub.-s-butyl 2,4-diCl.sub.2C.sub.6 H.sub.3305 .sub.-s-butyl 4-ClC.sub.6 H.sub.4306 4-ClC.sub.6 H.sub.4 3-CH.sub.34-ClC.sub.6 H.sub.5 175-176307 2,4-diClC.sub.6 H.sub.3 2,4-diClC.sub.6 H.sub.3 170308 2-NO.sub.2C.sub.6 H.sub.4 3-NO.sub.2C.sub.6 H.sub.4 170-172309 4-C.sub.2 H.sub.5 OC.sub.6 H.sub.4 4-C.sub.2 H.sub.5 OC.sub.6 H.sub.4 gum__________________________________________________________________________ *Includes 1 mole of ethanol occluded in the crystal lattice. .sup.+ Compounds 8 and 18 were obtained as polymorphs and this explains their different melting points. n-Pe = nPentyl n-He = nhexyl C.sub.3 H.sub.5 = cyclopropyl C.sub.4 H.sub.7 = cyclobutyl C.sub.5 H.sub.9 = cyclopentyl C.sub.6 H.sub.11 = cyclohexyl MO = morpholino Z = difluoromethylenedioxy
The compounds of general formula (I) may be produced by reacting a compound of general formula (II) or (III): ##STR6## in which R.sup.1 and R.sup.2 are as defined above and X is a halogen atom (preferably a chlorine or bromine atom), with 1,2,4-triazole either in the presence of an acid-binding agent or in the form of one of its alkali metal salts in a convenient solvent. Suitably the compound of general formula (II) or (III) is reacted at 20.degree.-100.degree. C. with the sodium salt of 1,2,4-triazole (the salt can be prepared by adding either sodium hydride or sodium methoxide to 1,2,4-triazole) in a convenient solvent such as acetonitrile, methanol, ethanol or dimethylformamide. The product can be isolated by pouring the reaction mixture into water and recrystallising the solid formed from a convenient solvent.
The compounds of general formula (II) and (III) can be prepared by reacting a compound of general formula (IVa) or (IVb): ##STR7## wherein R.sup.1, R.sup.2 and X are as defined above with, respectively, a Grignard compound of general formula (Va) or (Vb): ##STR8## wherein R.sup.1 and R.sup.2 are as defined above and Y us a halogen (preferably chlorine, bromine or iodine) in a convenient solvent such as diethyl ether or tetrahydrofuran. Generally a mixture of the compounds of general formula (II) and (III) are obtained. For example, when a compound of general formula (IVa) wherein R.sup.1 is alkyl or cycloalkyl is reacted, the compound of formula (II) generally predominates in the mixture; on the other hand, when R.sup.1 is optionally substituted phenyl, the compound of general formula (III) generally predominates in the mixture.
The compounds of general formula (IV) and (V) may be made by methods set out in the literature.
The compounds of general formula (II) wherein each of R.sup.1 and R.sup.2, which may be the same or different, is substituted phenyl may also be prepared by reacting the appropriate benzophenone compound of general formula (VI)
R.sup.1 --CO--R.sup.2
wherein R.sup.1 and R.sup.2 are as defined above, with dimethyl oxosulphonium methylide (Corey and Chaykovsky JACS, 1965, 87, 1353-1364) or dimethyl sulphonium methylide (Corey and Chaykovsky, JACS, 1962, 84, 3782) using methods set out in the literature.
The benzophenone compounds of general formula (VI) can be prepared, using the Friedel-Crafts reaction, by reacting a substituted benzoyl chloride with the appropriately substituted benzene in the presence of a Lewis acid e.g. aluminium chloride.
The compounds of general formula (II) wherein each of R.sup.1 is alkyl, cycloalkyl or optionally substituted phenyl and R.sup.2 is optionally substituted phenyl or optionally substituted benzyl can also be produced by reacting a .beta.-hydroxy selenide compound of general formula (VII) ##STR9## wherein R.sup.1 and R.sup.2 are as defined above, with methyl iodide in potassium t-butoxide according to the method of Van Ende, Dumont and Krief, Angew. Chem. Int. Ed., 1975, 14, 700.
The .beta.-hydroxy selenide compound can be prepared by treating the diselenide with the appropriate ketone in the presence of butyl lithium.
The compounds of general formula (III) wherein R.sup.1 is alkyl or cycloalkyl and R.sup.2 is optionally substituted benzyl (particularly benzyl ring substituted with alkoxy) can also be prepared by reacting a compound of general formula (VIII) ##STR10## wherein R.sup.1 and R.sup.2 are as defined above and Ar is aryl (e.g. phenyl) with an alkylating agent to give the corresponding sulphonium salt which is then reacted with 1,2,4-triazole in the form of an alkali metal (e.g. sodium or potassium) salt. The compound of general formula (VIII) can be prepared by methods known in the art.
The invention further provides, as useful intermediates, the compounds having the formulae: ##STR11## wherein R.sup.1 and R.sup.2 are as defined in any of the preceding claims and X is a halogen atom, especially chlorine.
In particular the invention provides a compound as defined above in the preceding paragraph wherein R.sup.1 and R.sup.2, which may be the same or different, are optionally substituted phenyl.
In a preferred aspect the invention provides as useful, novel, intermediates the compounds of formulae: ##STR12##
The salts and metal complexes of the compounds of general formula (I) can be prepared from the latter in known manner. For example, the complexes can be made by reacting the uncomplexed compound with a metal salt in a suitable solvent.
The compounds of general formula (I) are generally prepared by the above reactions in the form of racemic mixtures. The resolution of these mixtures into the constituent enantiomers can be performed by known methods. Examples of these methods are (1) forming the diastereoisomeric salts or esters of the compound of general formula (I) with an optically active acid (e.g. camphor sulphonic acid), separating the isomeric salts or esters and converting the separated isomeric salts or esters into the enantiomers of the compound of general formula (I); (2) forming the diastereoisomeric carbamates of the compound of general formula (I) by reacting a halo-formate (e.g. chloroformate) of the latter with an optically active amine (e.g. .alpha.-methylbenzylamine), separating the isomeric carbamates, and converting the separated isomeric carbamates into the enantiomers of the compound of general formula (I), reacting the hemiphthate with an optically active amine (e.g. .alpha.-methylbenzylamine) to give a salt of the hemiphthate, separating the isomeric salts and converting the separated salts into the enantiomers of the compound of general formula (I); or (4) resolving the mixtures using enantio-selective crystallisation techniques (Leigh, Chemistry and Industry, 1970, pages 1016-1017, and ibid, 1977, page 36). The separation of the diastereoisomeric salts, esters and carbamates can be achieved by for example crystallisation techniques or by high pressure liquid chromatography (HPLC). Alternatively, the enantiomers can be prepared directly from the compound of general formula (II) by stereospecific reduction, for example by biochemical reduction (using for example yeast or Aspergillus niger) or by hydrogenation using chiral catalysts (e.g. a Wilkinson's catalyst) or by reduction with borohydride/amino acid complexes.
The compounds, salts, andmetal complexes, are active fungicides, particularly against the diseases:
Piricularia oryzae on rice
Puccinia recondita, Puccinia striiformis and other rusts on wheat, Puccinia hordei, Puccinia striiformis and other rusts on barley, and rusts on other hosts e.g. coffee, apples, vegetables and ornamental plants
Plasmopara viticola on vines
Erysiphe graminis (powdery mildew) on barley and wheat and other powdery mildews on various hosts such as
Sphaerotheca fuliginea on cucurbits (e.g. cucumber), Podosphaera leucotricha on apples and Uncinula necator on vines
Helminthosporium spp. and Rhynchosporium spp. on cereals
Cercospora arachidicola on peanuts and other Cercospora species on for example sugar beet, bananas and soya beans
Botrytis cinerea (grey mould) on tomatoes, strawberries, vines and other hosts
Phytophthora infestans (late blight) on tomatoes
Venturia inaequalis (scab) on apples
Some of the compounds have also shown a broad range of activities against fungi in vitro. They have activity against various post-harvest diseases on fruit (e.g. Penicillium digatatum and italicum on oranges and Gloeosporium musarum on bananas). Further some of the compounds are active as seed dressings against: Fusarium spp., Septoria spp., Tilletia spp. (i.e. bunt, a seed borne disease of wheat), Ustilago spp., Helminthosporium spp. on cereals, Rhizoctonia solani on cotton and Corticium sasakii on rice.
The compounds can move acropetally in the plant tissue. Moreover, the compounds can be volatile enough to be active in the vapour phase against fungi on the plant.
They may also be useful as industrial (as opposed to agricultural) fungicides, e.g. in the prevention of fungal attack on wood, hides, leather and especially paint films.
The compounds can also have plant growth regulating activities.
The plant growth regulating effects of the compounds are manifested as for example a stunting or dwarfing effect on the vegetable growth of woody and herbaceous mono- and di-cotyledonous plants. Such stunting or dwarfing may be useful, for example, in peanuts, cereals and soya bean where reduction in stem growth may reduce the risk of lodging and may also permit increased amounts of fertiliser to be applied. The stunting of woody species is useful in controlling the growth of undergrowth under power lines etc. Compounds which induce stunting or dwarfing may also be useful in modifying the stem growth of sugar cane thereby increasing the concentration of sugar in the cane at harvest; in sugar cane, the flowering and ripening may be controllable by applying the compounds. Stunting of peanuts can assist in harvesting. Growth retardation of grasses can help maintenance of grass swards. Examples of suitable grasses are Stenotaphrum secundatum (St. Augustine grass), Cynosurus cristatus, Lolium multiflorum and perenne, Agrostis tenuis, Cynodon dactylon (Bermuda grass), Dactylis glomerata, Festuca spp. (e.g. Festuca rubra) and Poa spp. (e.g. Poa pratense). The compounds may stunt grasses without significant phytotoxic effects and without deleteriously affecting the appearance (particularly the colour) of the grass; this makes such compounds attractive for use on ornamental lawns and on grass verges. They may also have an effect on flower head emergence in for example grasses. The compounds can also stunt weed species present in the grasses; examples of such weed species are sedges (e.g. Cyperus spp.) and dicotyledonous weeds (e.g. daisy, plantain, knotweed, speedwell, thistle, docks and ragwort). The growth of non-crop vegetation (e.g. weeds or cover vegetation) can be retarded thus assisting in the maintenance of plantation and field crops. In fruit orchards, particularly orchards subject to soil erosion, the presence of grass cover is important. However excessive grass growth requires substantial maintenance. The compounds of the invention could be useful in this situation as they could restrict growth without killing the plants which would lead to soil erosion; at the same time the degree of competition for nutrients and water by the grass would be reduced and this could result in an increased yield of fruit. In some cases, one grass species may be stunted more than another grass species; this selectivity could be useful for example for improving the quality of a sward by preferential suppression of the growth of undesirable species.
The dwarfing may also be useful in miniaturising ornamental, household, garden and nursery plants (e.g. poinsettias, chrysanthemums, carnations, tulips and daffodils).
As indicated above, the compounds can also be used to stunt woody species. This property can be used to control hedgerows or to shape fruit trees (e.g. apples). Some coniferous trees are not significantly stunted by the compounds so the compounds could be useful in controlling undesirable vegetation in conifer nurseries.
The plant growth regulating effect may (as implied above) manifest itself in an increase in crop yield.
In the potato, vine control in the field and inhibition of sprouting in the store may be possible.
Other plant growth regulating effects caused by the compounds include alteration of leaf angle and promotion of tillering in monocotyledonous plants. The former effect may be useful for example in altering the leaf orientation of, for example, potato crops thereby letting more light into the crops and inducing an increase in phytosynthesis and tuber weight. By increasing tillering in monocotyledonous crops (e.g. rice), the number of flowering shoots per unit area may be increased thereby increasing the overall grain yield of such crops. In grass swards an increase in tillering could lead to a denser sward which may result in increased resilience in wear.
The treatment of plants with the compounds can lead to the leaves developing a darker green colour.
The compounds may inhibit, or at least delay, the flowering of sugar beet and thereby may increase sugar yield. They may also reduce the size of sugar beet without reducing significantly the sugar yield thereby enabling an increase in planting density to be made. Similarly in other root crops (e.g. turnip, swede, mangold, parsnip, beetroot, yam and cassava) it may be possible to increase the planting density.
The compounds could be useful in restricting the vegetative growth of cotton thereby leading to an increase in cotton yield.
The compounds may be useful in rendering plants resistant to stress since the compounds can delay the emergence of plants grown from seed, shorten stem height and delay flowering; these properties could be useful in preventing frost damage in countries where there is significant snow cover in the winter since then the treated plants would remain below snow cover during the cold weather. Further the compounds may cause drought or cold resistance in certain plants.
When applied as seed treatments at low rates the compounds can have a growth stimulating effect on plants.
In carrying out the plant growth regulating method of the invention, the amount of compound to be applied to regulate the growth of plants will depend upon a number of factors, for example the particular compound selected for use, and the identity of the plant species whose growth is to be regulated. However, in general an application rate of 0.1 to 15, preferably 0.1 to 5, kg per hectare is used. However, on certain plants even application rates within these ranges may give undesired phytotoxic effects. Routine tests may be necessary to determine the best rate of application of a specific compound for any specific purpose for which it is suitable.
The compounds may be used as such for fungicidal or plant growth regulating purposes but are more conveniently formulated into compositions for such usage. The invention thus provides also a fungicidal or plant growth regulating composition comprising a compound which is an enantiomer of the invention or an ester, salt or complex thereof, and a carrier or diluent.
The invention also provides a method of combating fungi, which comprises applying to a plant, to seed of a plant or to the locus of a plant or seed, a compound which is an enantiomer of the invention or an ester, salt or complex thereof.
The invention also provides a method of regulating plant growth which comprises applying to a plant, to seed of a plant or to the locus of a plant or seed, a compound which is an enantiomer of the invention or an ester, salt or complex thereof as hereinbefore defined.
The compounds can be applied in a number of ways, for example they can be formulated or unformulated, directly to the foliage of a plant, to seeds or to other medium in which plants are growing or are to be planted, or they can be sprayed on, dusted on or applied as a cream or paste formulation, or they can be applied as a vapour. Application can be to any part of the plant, bush or tree, for example to the foliage, stems, branches or roots, or to soil surrounding the roots, or to the seed before it is planted.
The term "plant" as used herein includes seedlings, bushes and trees. Furthermore, the fungicidal method of the invention includes preventative, protectant, prophylactic and eradicant treatment.
The compounds are preferably used for agricultural and horticultural purposes in the form of a composition. The type of composition used in any instance will depend upon the particular purpose envisaged.
The compositions may be in the form of dusting powders or granules comprising the active ingredient and a solid diluent or carrier, for example fillers such as kaolin, bentonite, kieselguhr, dolomite, calcium carbonate, talc, powdered magnesia, Fuller's earth, gypsum, Hewitt's earth, diatomaceous earth and China clay. Such granules can be preformed granules suitable for application to the soil without further treatment. These granules can be made either by impregnating pellets of filler with the active ingredient or by pelleting a mixture of the active ingredient and powdered filler. Compositions for dressing seed, for example, may comprise an agent (for example a mineral oil) for assisting the adhesion of the composition to the seed; alternatively the active ingredient can be formulated for seed dressing purposes using an organic solvent (for example N-methylpyrrolidone or dimethylformamide).
The compositions may also be in the form of dispersible powders, granules or grains comprising a wetting agent to facilitate the disperion in liquids of the powder or grains which may contain also fillers and suspending agents.
The aqueous dispersions or emulsions may be prepared by dissolving the active ingredient(s) in an organic solvent optionally containing wetting, dispersing or emulsifying agent(s) and then adding the mixture to water which may also contain wetting, dispersing or emulsifying agent(s). Suitable organic solvents are ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, the xylenes, trichloroethylene, furfuryl alcohol, tetrahydrofurfuryl alcohol, and glycol ethers (e.g. 2-ethoxyethanol and 2-butoxyethanol).
The compositions to be used as sprays may also be in the form of aerosols wherein the formulation is held in a container under pressure in the presence of a propellant, e.g. fluorotrichloromethane or dichlorodifluoromethane.
The compounds can be mixed in the dry state with a pyrotechnic mixture to form a composition suitable for generating in enclosed spaces a smoke containing the compounds.
Alternatively, the compounds may be used in a microencapsulated form.
By including suitable additives, for example additives for improving the distribution, adhesive power and resistance to rain on treated surfaces, the different compositions can be better adapted for various utilities.
The compounds can be used as mixtures with fertilisers (e.g. nitrogen-, potassium- or phosphorous-containing fertilisers). Compositions comprising only granules of fertiliser incorporating, for example coated with, the compound, are preferred. Such granules suitably contain up to 25% by weight of the compound. The invention therefore also provides a fertiliser composition comprising a compound as hereinbefore defined.
The compositions may also be in the form of liquid preparations for use as dips or sprays which are generally aqueous dispersions or emulsions containing the active ingredient in the presence of one or more surfactants e.g. wetting agent(s), dispersing agent(s), emulsifying agent(s) or suspending agent(s). These agents can be cationic, anionic, or non-anionic agents. Suitable cationic agents are quaternary ammonium compounds, for example cetyltrimethylammonium bromide.
Suitable anionic agents are soaps, salts of aliphatic monoesters of sulphuric acid (for example sodium lauryl sulphate), and salts of sulphonated aromatic compounds (for example sodium dodecylbenzenesulphonate, sodium, calcium or ammonium lignosulphonate, butylnaphthalene sulphonate, and a mixture of sodium diisopropyl- and triisopropyl-naphthalene sulphonates).
Suitable non-ionic agents are the condensation products of ethylene oxide with fatty alcohols such as oleyl or cetyl alcohol, or with alkyl phenols such as octyl- or nonyl-phenol and octylcresol. Other non-ionic agents are the partial esters derived from long chain fatty acids and hexitol anhydrides, the condensation products of the said partial esters with ethylene oxide, and the lecithins. Suitable suspending agents are hydrophilic colloids (for example polyvinylpyrrolidone and sodium carboxymethylcellulose), and the vegetable gums (for example gum acacia and gum tragacanth).
The compositions for use as aqueous dispersions or emulsions are generally supplied in the form of a concentrate containing a high proportion of the active ingredient(s), the concentrate to be diluted with water before use. These concentrations often should be able to withstand storage for prolonged periods and after such storage be capable of dilution with water in order to form aqueous preparations which remain homogenous for a sufficient time to enable them to be applied by conventional spray equipment. The concentrates may conveniently contain up to 95%, suitably 10-85%, for example 25-60%, by weight of the active ingredient(s). These concentrates suitably contain organic acids (e.g. alkaryl or aryl sulphonic acids such as xylene-sulphonic acid or dodecylbenzenesulphonic acid) since the presence of such acids can increase the solubility of the active ingredient(s) in the polar solvents often used in the concentrates. The concentrates suitably contain also a high proportion of surfactants so that sufficiently stable emulsions in water can be obtained. After dilution to form aqueous preparations, such preparations may contain varying amounts of the active ingredient(s) depending upon the intended purpose, but an aqueous preparation containing 0.0005% or 0.01% to 10% by weight of active ingredient(s) may be used.
The compositions of this invention can comprise also other compound(s) having biological activity, e.g. compounds having similar or complementary fungicidal or plant growth regulating activity or compounds having herbicidal or insecticidal activity.
The other fungicidal compound can be for example one which is capable of combating ear diseases of cereals (e.g. wheat) such as Septoria, Gibberella and Helminthosporium spp., seed and soil borne diseases and downy and powdery mildews on grapes and powdery mildew and scab on apple etc. These mixtures of fungicides can have a broader spectrum of activity than the compound of general formula (I) alone; further the other fungicide can have a synergistic effect on the fungicidal activity of the compound of the general formula (I). Examples of the other fungicidal compound are imazalil, benomyl, carbendazim, thiophanate-methyl, captafol, captan, sulphur, triforine, dodemorph, tridemorph, pyrazophos, furalaxyl, ethirimol, dimethirimol, bupirimate, chlorothalonil, vinclozolin, procymidone, iprodione, metalaxyl, fosetyl-aluminium, carboxin, oxycarboxin, fenarimol, nuarimol, fenfuram, methfuroxam, nitrotalisopropyl, triadimefon, thiabendazole, etridiazole, triadimenol, biloxazol, dithianon, binapacryl, quinomethionate, quazatine, dodine, fentin acetate, fentin hydroxide, dinocap, folpet, diclofluanid, ditalimphos, kitazin, fenpropemorph, cycloheximide, dichlobutrazol, a dithiocarbamate, a copper compound, a mercury compound, DPX 3217, RH 2161, Chevron RE 20615, CGA 64250, CGA 54251 and RO 14-3169.
The compounds of general (I) can be mixed with soil, peat or other rooting media for the protection of plants against seed-borne, soil-borne or foliar fungal diseases.
Suitable insecticides are pirimor, croneton, dimethoate, metasystox and formothion.
The other plant growth regulating compound can be one which controls weeds or seedhead formation, improves the level or longevity of the plant growth regulating activity of the compounds of general formula (I), selectively controls the growth of the less desirable plants (e.g. grasses) or causes the compound of general formula (I) to act faster or slower as a plant growth regulating agent. Some of the other agents will be herbicides. Examples of suitable agents are the gibberellins (e.g. GA.sub.3, GA.sub.4 or GA.sub.7), the auxins (e.g. indoleacetic acid, indolebutyric acid, naphthoxyacetic acid or naphthylacetic acid), the cytokinins (e.g. kinetin, diphenylurea, benzimidazole, benzyladenine or BAP), phenoxyacetic acids (e.g. 2,4-D or MCPA), substituted benzoic acids (e.g. TIBA), morphactins (e.g. chlorfluorecol), maleic hydrazide, glyphosate, glyphosine, long chain fatty alcohols and acids (e.g. Off Shoot O or Off Shoot T), dikegulac, Sustar, Embark, substituted quaternary ammonium and phosphonium compounds (e.g. CCC or Phosfon-D), Ethrel, carbetamide, Racuza, Alar, asulam, abscissic acid, isopyrimol, RH531, hydroxybenzonitriles (e.g. bromoxynil), Avenge, Suffix, Lontrel or thiocarbamates (e.g. Eptam).





The following Examples illustrate the invention; the temperatures are given in degrees Centigrade (.degree.).
EXAMPLE 1
This Example illustrates the preparation of: 1-(1,2,4-Triazol-1-yl)-2,3-diphenyl-propan-2-ol (Compound No 1 of Table I).
Benzyl chloride (0.2 mol) was dissolved in dry diethyl ether (200 ml) and added dropwise to magnesium turnings (0.22 g atoms). After all the magnesium had reacted, the solution was refluxed for 1 hour and cooled to room temperature. Phenacyl chloride (0.1 mol) in dry diethyl ether (100 ml) was added dropwise over 1 hour at such a rate as to maintain gentle reflux. The solution was then refluxed for 2 hours, and cooled to room temperature; the mixture was poured into ice and the complex decomposed with ammonium chloride solution. The ethereal solution was washed several times with water (2.times.200 ml), dried (Na.sub.2 SO.sub.4), and the solvent removed in vacuo to give, as a colourless oil, the crude chlorohydrin which was dissolved in dimethyl formamide (80 ml) and a solution of sodium triazole [prepared from sodium (0.1 g atoms) in methanol (40 ml) and 1,2,4-triazole (0.1 mol)] added dropwise at room temperature. After stirring at room temperature for 2 hours, the solution was warmed at 50.degree. for 3 hours. The solvent was removed in vacuo and the residue poured into water to give a crystalline solid which was recrystallised from ethanol/petroleum ether to give the title compound, m.p. 124.5.degree..
EXAMPLE 2
This Example illustrates the preparation of: 1-(1,2,4-Triazol-1-yl)-2-phenyl-3-p-fluorophenyl-propan-2-ol (Compound No 3 of Table I).
p-Fluorobenzyl chloride (0.1 mol) in dry diethyl ether (100 ml) was added dropwise to magnesium turnings (0.11 g atoms) and the solution was stirred vigorously until refluxing occurred. When all the magnesium had reacted, the solution was refluxed for a further 1 hour and then cooled to room temperature. Phenacyl chloride (0.05 mol) in dry diethyl ether (50 ml) was added dropwise to the solution over 1 hour at such a rate as to maintain gentle reflux. The mixture was refluxed for 2 hours, cooled to room temperature and the mixture poured into ice/ammonium chloride solution to decompose the complex. The ethereal solution was washed several times with water (2.times.200 ml), dried (Na.sub.2 SO.sub.4), and the solvent removed in vacuo to give, as a colourless oil, the crude chlorohydrin. The latter was dissolved in dimethyl-formamide (40 ml) and a solution of sodium triazole [prepared from sodium (0.05 g atoms) in methanol (20 ml) and 1,2,4-triazole (0.05 mol)] added dropwise at room temperature. After stirring at room temperature for 2 hours, the solution was warmed at 50.degree. for 3 hours. The solvent was removed in vacuo and the mixture poured into water to give a crystalline solid which was recrystallised from petroleum ether/chloroform to give the title compound, m.p. 116-8.degree..
EXAMPLE 3
This Example illustrates the preparation of: 1,1-Diphenyl-2-(1,2,4-triazol-1-yl)-ethan-1-ol (Compound No 17 of Table I).
Stage 1. Bromobenzene (0.2 mol, 31.4 g) in sodium dry diethyl ether (200 ml) was added dropwise to magnesium (0.22 gram atoms, 5.3 g). After all the magnesium had reacted, phenacyl chloride (0.1 mol, 15.5 g) in diethyl ether (100 ml) was added dropwise to the solution stirred at room temperature for 1 hour. The reaction mixture was poured into saturated ammonium chloride solution, washed with water (3.times.150 ml), and dried (Na.sub.2 SO.sub.4). Removal of the ether gave a pale yellow oil which solidified on standing. Recrystallisation from the petroleum ether (60.degree.-80.degree.) gave 1,1-diphenyl-2-chloro-ethan-1-ol (60%) as a white crystalline solid, m.p. 56.degree.-57.degree..
Stage 2. 1,2,4-Triazole (0.03 mol, 2.07 g) was added portionwise to a suspension of sodium hydride (0.03 mol, 0.72 g) in DFM (30 ml) and the solution stirred until effervescence ceased. 1,2-Diphenyl-2-chloro-ethan-1-ol (0.015 mol, 2.94 g) in dimethylformamide (DMF; 10 ml) was added dropwise and the solution warmed at 100.degree. for six hours. The reaction mixture was poured into water and a white solid crystallised out. This was filtered off, washed with water, dried, and recrystallised from ethanol to give the title compound as a white crystalline solid, m.p. 128.degree.-129.degree..
EXAMPLE 4
This Example illustrates the preparation of: 2-Methyl-4-phenyl-5-(1,2,4-triazol-1-yl)-pentan-4-ol (Compound No 31 of Table I).
Stage 1. The Grignard reagent generated from isobutyl bromide (0.1 mol, 13.7 g) in sodium dry diethyl ether (50 ml) and magnesium turnings (0.11 g atoms; 2.6 g) was added dropwise to a solution of phenacyl chloride (0.05 mol, 7.7 g) in sodium dry diethyl ether (100 ml) so that gentle reflux was maintained. The solution was then stirred at room temperature for 1 hour and the magnesium complex destroyed by pouring into a saturated ammonium chloride solution (200 ml). The ethereal extract was washed with water (3.times.150 ml) and dried (Na.sub.2 SO.sub.4). Removal of the solvent gave a colourless liquid which distilled at reduced pressure to give 2-methyl-4-phenyl-5-chloro-pentan-4-ol (70%), b.p. 86.degree.-88.degree./0.01 mm Hg.
Stage 2. 1,2,4-Triazole (0.03 mol, 2.07 g) was added portionwise in 100% sodium hydride (0.03 mol, 0.72 g) in dry DMF (30 ml) and stirred at room temperature until the effervescence ceased. 2-Methyl-4-phenyl-5-chloro-pentan-4-ol (0.01 mol, 2.1 g) in dry DMF 10 ml) was added dropwise at room temperature and then the solution was stirred at 100.degree. l for 6 hours. On cooling to room temperature the solution was poured into water to precipitate out a solid which was recrystallised from petroleum (60.degree.-80.degree.)/chloroform giving the title compound (60%) as a white crystalline solid, m.p. 94.degree.-95.degree..
EXAMPLE 5
1-(1,2,4-Triazol-1-yl)-2-o-chlorophenyl-2-p-fluorophenyl-ethan-2-ol (Compound No 45 of Table I).
A solution of dimethyl oxosulphonium methylide was prepared under nitrogen from sodium hydride (0.03 mol) and powdered trimethyl oxosulphonium iodide (0.03 mol) in dry dimethylsulphoxide (DMSO; 30 ml). A solution of o-chlorophenyl p-fluorophenyl ketone (0.025 mol) in DMSO (10 ml) was added dropwise at room temperature. The solution was then heated at 50.degree. for 1.5 hours, cooled to room temperature and poured into water. The solution was extracted with diethyl ether (100 ml), washed with water (3.times.100 ml), and dried over anhydrous sodium sulphate. Removal of the solvent gave 1-o-chlorophenyl-1-p-fluorophenyl ethylene oxide (90%) as a colourless liquid.
1,2,4-Triazole (0.04 mol) was added portionwise to sodium hydride (0.04 mol) in DMF (40 ml) and the solution stirred at room temperature until effervescence ceased. 1-o-Chlorophenyl-1-p-fluorophenyl ethylene oxide (0.02 mol) in DMF (10 ml) was added dropwise and the solution stirred at 80.degree. for 4 hours. The solution was poured into water and triturated with petroleum ether to give a white crystalline solid which was filtered off and dried. Recrystallisation from petroleum ether (60.degree.-80.degree.)/methylene chloride gave the title compound (70%) as a white crystalline solid, m.p. 115.degree.-116.degree..
EXAMPLE 6
This Example illustrates the preparation of: 2,2-Dimethyl-3-(2-methoxybenzyl)-4-(1,2,4-triazol-1-yl)-butan-3-ol (Compound No 130 of Table I).
Stage 1. Potassium t-butoxide (19 g) was dissolved in dimethylsulphoxide (200 ml; dried by distilling from calcium hydride and sodamide) and pinacolone (15 g; freshly distilled from calcium hydride) was added under argon to give a yellow solution. o-Methoxyphenyl iodide (10 g) was then added and a brown colour rapidly developed. The solution was stirred for 1.5 hours before pouring into water (1 liter), acidifying the mixture with 2M hydrochloric acid and extracting it with diethyl ether. Evaporation of the dried (MgSO.sub.4) ethereal solution gave a yellow liquid (11.8 g) b.p. 88.degree.-93.degree. C./0.9 mm. The distillate solidified to give 2,2-dimethyl-4-(o-methoxy-phenyl)butan-3-one (6 g).
Stage 2. Thioanisole (3.3 g) was added to diazobicyclooctane (3.5 g) in dry tetrahydrofuran (THF) under argon and the colourless solution was cooled in an ice/salt bath. 1.6M-butyl lithium solution (20 ml) in hexane was then added over 10 minutes at 0.degree. to 2.degree. C. After stirring the yellow solution for 15 minutes, a solid was precipitated. The mixture was stirred for a further 45 minutes in the ice bath and then it was allowed to warm up to room temperature. The mixture was then cooled in the ice bath and a solution of the product (5 g) of stage 1 in dry THF (25 ml) was added at 0.degree. to 5.degree. C. When the addition was complete, the resultant yellow solution was allowed to stand overnight, poured into water, acidified with 2M-hydrochloric acid and extracted with diethyl ether. The ethereal solution was washed well with water, dried (MgSO.sub.4) and evaporated to give a yellow liquid (8.8 g) which solidified on standing. Recrystallisation from petroleum ether (60.degree.-80.degree.) gave 2,2-dimethyl-3-hydroxy-3-(o-methoxybenzyl)-4-thiophenylbutane (3.1 g), m.p. 74.degree.-75.degree. C.
Stage 3. The product (2.5 g) of Stage 2 was added to a stirred suspension of trimethyl oxonium tetrafluoroborate (1.3 g) in methylene chloride (25 ml). After about 1 hour a clear solution was obtained. The solvent was then removed on the rotavaporator to give a pale organe gum, which was dissolved in dry DMF (10 ml) and the solution added to a solution of 1,2,4-triazole sodium salt (1.2 g) in DMF (15 ml). [The solution was prepared by washing sodium hydride with dry diethyl ether, suspending it in dry DMF and adding the triazole]. The reaction mixture was then stirred at 120.degree. C. for 2.5 hours. The reaction mixture was then quenched by pouring into water (100 ml) and the emulsion was extracted with diethyl ether (3.times.50 ml). The ethereal solution was washed well with water, dried (MgSO.sub.4) and evaporated to give a pale yellow liquid. The mixture was subjected to dry column chromatography on silica eluting with diethyl ether to give a colourless liquid which solidified on trituration with diethyl ether. Recrystallation from petroleum ether (60.degree.-80.degree.) gave the title compound (0.5 g; 23%), m.p. 113.degree.-116.degree..
EXAMPLE 7
This Example illustrates the preparation of: 1-(1,2,4-Triazol-1-yl)-2-(2-chloro-4-methoxy-phenyl)-2-(4-fluoro-phenyl)-ethan-2-ol (Compound No 294 of Table I).
Stage 1. 3-chloroanisole (0.1 mol) was added dropwise to a suspension of aluminium chloride (0.11 ml) in carbon disulphide (40 ml) at room temperature and stirred for 30 minutes until it had dissolved. The mixture was cooled in ice and 4-fluorobenzoyl chloride (0.1 mol) added dropwise. After complete addition the solution was stirred for 1 hour at room temperature and refluxed for 1 hour. The solution was poured into ice (200 ml), containing CHCl (20 ml), extracted with ether (200 ml), washed with water (3.times.150 ml), and dried over anhydrous sodium sulphonate. Removal of the solvent gave an oil which was purified by column chromatography silica K6O eluted with toluene/petrol 1:1 to give (2-chloro-4-methoxy-phenyl)-4-fluorophenyl-ketone (40%) as colourless crystalline solid m.p. 31.degree..
Stage 2. A solution of dimethyl sulphonium methylide was prepared under nitrogen at 0.degree. C. from sodium hydride (0.03 mol using 80% suspension in oil), trimethyl sulphonium iodide (0.03 mol) in dry dimethyl sulphoxide (30 ml) and dry tetrahydrofuran (30 ml). A solution of (2-chloro-4-methoxyphenyl)-4-fluorophenyl ketone (0.02 mol) in tetrahydrofuran (20 ml) was added at 0.degree., stirred for 30 minutes at 0.degree., and allowed to warm-up to room temperature. The solution was poured into water, extracted with diethyl ether (150 ml), washed with water (3.times.100 ml) and dried over anhydrous magnesium sulphate. Removal of the solvent gave 1-(2-chloro-4-methoxy-phenyl)-1-(4-fluorophenyl)-ethylene oxide (90%) as a colourless oil. Stage 3. 1,2,4-Triazole (0.03 mol) was added portionwise to sodium hydride (0.03 mol) in dimethyl formamide (30 ml) and the solution was stirred at room temperature until the effervescence ceased. 1-(2-chloro-4-methoxyl-phenyl)-1-(4-fluorophenyl)-ethylene oxide (0.015 mol) in dimethyl formamide (10 ml) was added dropwise and the solution stirred at 80.degree. for 4 hours. The solution was poured into water and triturated with petroleum ether to an off-white solid which was filtered off and dried. Recrystallisation from petroleum ether/chloroform gave the title compound (65%) as a white crystalline solid m.p. 138.degree.-140.degree..
EXAMPLE 8
This Example illustrates the preparation of: 1-(1,2,4-Triazol-1-yl)-2-(4-chlorophenyl)-3,3-dimethyl-butan-2-ol (Compound No 196 of Table I).
Stage 1. Trimethyl acetonitrile (0.1 mol) in dry tetrahydrofuran (50 ml) was added dropwise with stirring to the Grignard reagent prepared form 4-chloro-iodobenzene (0.11 mol) and magnesium turnings (0.11 g atoms) in sodium dry ether (50 ml) at such a rate as to retain gentle reflux. The solution was refluxed for 4 hours, cooled to room temperature, and water (40 ml) added carefully. 2N H.sub.2 SO.sub.4 (50 ml) was added and the ether solution washed with water (3.times.100 ml) and dried over anhydrous magnesium sulphate. Removal of the solvent gave a yellow oil which was distilled at the water pump to give tertiary butyl 4-chlorophenyl ketone (40%) as a colourless liquid b.p. 116.degree.-128.degree./15 mm Hg.
Stage 2. A solution of dimethyl oxosulphonium methylide was prepared under nitrogen from sodium hydride (0.03 mol) and powdered trimethyl oxosulphonium iodide (0.03 mol) in dry dimethyl sulphoxide (40 ml). A solution of 4-chlorophenyl tertiary butyl ketone (0.025 mol) in dry dimethyl sulphoxide (10 ml) was added dropwise at room temperature and the solution heated at 50.degree. C. for 2.5 hours. After cooling to room temperature the solution was extracted with ether (150 ml), washed with water and dried over anhydrous sodium sulphate. Removal of the solvent gave 1-(4-chlorophenyl)-1-t-butyl-ethylene oxide (95%) as a colourless liquid.
Stage 3. 1,2,4-Triazole (0.04 mol) was added portionwise to sodium hydride (0.04 mol) in dimethyl formamide (40 ml) and the solution stirred at room temperature until the effervescence ceased. 1-(4-chlorophenyl)-1-t-butyl-ethylene oxide (0.02 mol) in dimethyl formamide (10 ml) was added dropwise and the solution stirred at 60.degree. for 3 hours. The solution was poured into water and triturated with petroleum ether to give a white solid which recrystallised from 60/80 petroleum ether gave the title compound (65%) m.p. 70.degree.-3.degree..
EXAMPLE 9
This Example illustrates the preparation of: 1-(1,2,4-Triazol-1-yl)-bis-2-(4-fluorophenyl)-2-methoxy-ethane.
Stage 1. A solution of dimethyl oxosulphonium methylide was prepared under nitrogen from sodium hydride (0.1 mol) and powdered trimethyl oxosulphonium iodide (0.1 mol) in dry dimethyl sulphoxide (100 ml). A solution of 4,4'-difluorobenzophenone (0.08 mol) in dimethyl sulphoxide (40 ml) was added dropwise at room temperature and the solution heated at 50.degree. for 2 hours. After cooling to room temperature the solution was extracted with diethyl ether (400 ml), washed with water (3.times.250 ml), and dried over anhydrous sodium sulphate. Removal of the solvent gave 1,1-bis-(4-fluorophenyl)-ethylene oxide (95%) as a colourless oil.
Stage 2. 1,2,4-Triazole (0.1 mol) was added portionwise to sodium hydride (0.1 mol) in dimethyl formamide (100 ml) and the solution stirred at room temperature until the effervescence ceased. 1,1-bis-(4-fluorophenyl)-ethylene oxide (0.05 mol) in dimethyl formamide (25 ml) was added dropwise and the solution stirred at 80.degree. for 4 hours. The solution was poured into water and triturated with petroleum ether to give a white crystalline solid which was filtered off and dried. Recrystallisation from petroleum ether (60.degree.-80.degree.)/chloroform gave 1-(1,2,4-triazole-1-yl)-bis-2-(4-fluorophenyl)-ethan-2-ol (70%) as a white crystalline solid m.p. 170.degree.-1.degree..
Stage 3. Sodium hydride (0.02 mol) was suspended in dry tetrahydrofuran (50 ml) and 1-(1,2,4-triazol-1-yl)-bis-2-(4-fluorophenyl)-ethan-2-ol (0.02 mol) added portionwise at room temperature. The solution was warmed to 50.degree. to complete the reaction. After cooling to room temperature methyl iodide (0.04 mol) was added dropwise at 20.degree. and the reaction stirred at room temperature for 24 hours. The reaction was poured into water (100 ml), extracted with diethyl ether (150 ml), washed with water (2.times.100 ml), and dried over anhydrous sodium sulphate. Removal of the solvent gave an oil which solidified on standing. Recrystallisation from petroleum-ether/chloroform gave the title compound (90%) as a white crystalline solid. m.p. 100.degree..
EXAMPLE 10
An emulsifiable concentrate was made up by mixing the ingredients, and stirring the mixture until all the constituents were dissolved.
______________________________________Compound of Example 1 10%Ethylene dichloride 40%Calcium dodecylbenzenesulphate 5%"Lubrol" L 10%"Aromasol" H 35%______________________________________
EXAMPLE 11
A composition in the form of grains readily dispersible in a liquid, e.g. water, was prepared by grinding together the first three ingredients in the presence of added water and then mixing in the sodium acetate. The resultant mixture was dried and passed through a British Standard mesh sieve, size 44-100, to obtain the desired size of grains.
______________________________________Compound of Example 2 50%"Dispersol" T 25%"Lubrol" APN5 1.5%Sodium acetate 23.5%______________________________________
EXAMPLE 12
The ingredients were all ground together to produce a powder formulation readily dispersible in liquids.
______________________________________Compound of Example 3 45%"Dispersol" T 5%"Lissapol" NX 0.5%"Cellofas" B600 2%Sodium acetate 47.5%______________________________________
EXAMPLE 13
The active ingredient was dissolved in a solvent and the resultant liquid was sprayed on to the granules of China clay. The solvent was then allowed to evaporate to produce a granular composition.
______________________________________Compound of Example 4 5%China clay granules 95%______________________________________
EXAMPLE 14
A composition suitable for use as a seed dressing was prepared by mixing the three ingredients.
______________________________________Compound of Example 1 50%Mineral oil 2%China clay 48%______________________________________
EXAMPLE 15
A dusting powder was prepared by mixing the active ingredient with talc.
______________________________________Compound of Example 2 5%Talc 95%______________________________________
EXAMPLE 16
A Col formulation was prepared by ball-milling the constituents set out below and then forming an aqueous suspension of the ground mixture with water.
______________________________________Compound of Example 3 40%"Dispersol" T 10%"Lubrol" APN5 1%Water______________________________________
EXAMPLE 17
A dispersible powder formulation was made by mixing together the ingredients set out below and then grinding the mixture until all were thoroughly mixed.
______________________________________Compound of Example 4 25%"Aerosol" OT/B 2%"Dispersol" A.C. 5%China clay 28%Silica 40%______________________________________
EXAMPLE 18
This Example illustrates the preparation of a dispersible powder formulation. The ingredients were mixed and the mixture then ground in a comminution mill.
______________________________________Compound of Example 1 25%"Perminal" BX 1%"Dispersol" T 5%Polyvinylpyrrolidone 10%Silica 25%China clay 34%______________________________________
EXAMPLE 19
The ingredients set out below were formulated into a dispersible powder by mixing then grinding the ingredients.
______________________________________Compound of Example 2 25%"Aerosol" OT/B 2%"Dispersol" A 5%China clay 68%______________________________________
In Examples 10 to 19 the proportions of the ingredients given are by weight.
There now follows an explanation of the compositions or substances represented by the various Trade Marks and Trade Names mentioned above.
______________________________________LUBROL L: a condensate of nonyl phenol 1 mole) with ethylene oxide (13 moles)ARMASOL H: a solvent mixture of alkylbenzenesDISPERSOL T & AC: a mixture of sodium sulphate and a condensate of formaldehyde with sodium naphthalene sulphonateLUBROL APN5: a condensate of nonyl phenol (1 mole) with naphthalene oxide (5.5 moles)CELLOFAS B600: a sodium carboxymethyl cellulose thickenerLISSAPOL NX: a condensate of nonyl phenol (1 mole) with ethylene oxide (8 moles)AEROSOL OT/B: dioctyl sodium sulphosuccinatePERMINAL BX: a sodium alkyl naphthalene sulphonate______________________________________
EXAMPLE 20
The compounds were tested against a variety of foliar fungal diseases of plants. The technique employed was as follows.
The plants were grown in John Innes Potting Compost (No 1 or 2) in 4 cm diameter minipots. A layer of fine sand was placed at the bottom of the pots containing the dicotyledonous plants to facilitate uptake of test compound by the roots. The test compounds were formulated either by bead milling with aqueous Disperson T or as a solution in acetone or acetone/ethanol which was diluted to the required concentration immediately before use. For the foliage diseases, suspension (100 ppm active ingredient) were sprayed on to the soil. Exceptions to this were the tests on Botrytis cinerea, Plasmopara viticola and Venturia inaequalis. The sprays were applied to maximum retention and the root drenches to a final concentration equivalent to approximately 40 ppm a.i./dry soil. Tween 20, to give a final concentration of 0.05%, was added when the sprays were applied to cereals.
For most of the tests the compound was applied to the soil (roots) and to the foliage (by spraying) one or two days before the plant was inoculated with the diseases. An exception was the test on Erysiphe graminis in which the plants were inoculated 24 hours before treatment. After inoculation, the plants were put into an appropriate environment to allow infection to take place and then incubated until the disease was ready for assessment. The period between inoculation and assessment varied from four to fourteen days according to the disease and environment.
The disease control was recorded by the following grading:
4=no disease
3=trace--5% of disease on untreated plants
2=6-25% of disease on untreated plants
1=26-59% of disease on untreated plants
0=60-100% of disease on untreated plants
The results are shown in Table II. A dash in the table thus "-" signifies that no test against the disease was conducted.
TABLE II__________________________________________________________________________COM- PIRI- PLASMO- PHYTO- CERCOSPORA VENTURIAPOUND PUCCINIA ERYSIPHE CULARIA PARA PHTHORA BOTRYTIS ARACHI- INAE-NUM- RECONDITA GRAMINIS ORYZAE VITICOLA INFESTANS CINEREA DICOLA QUALISBER (WHEAT) (BARLEY) (RICE) (VINE) (TOMATO) (TOMATO) (PEANUT) (APPLE)__________________________________________________________________________ 1 4 4 1 0 0 3 4 3 2 4 4 0 0 0 3 3 -- 3 4 4 1 0 0 3 4 3 4 3 4 0 4 0 3 4 3 5 4 4 1 4 0 3 3 4 5 4 4 3 2 0 3 4 -- 8 4 -- 3 4 3 3 4 3 9 3 4 2 0 0 2 3 310 4 4 3 0 -- 3 4 411 4 4 3 0 1 4 4 412 4 4 -- 0 0 4 4 413 4 4 3 3 0 3 4 314 4 4 1 0 1 4 4 315 4 4 1 0 2 3 4 316 4 4 4 0 0 3 4 017 -- 4 -- 0 0 1 4 418 4 -- 3 0 0 3 4 319 4 4 3 3 0 -- 4 420 4 4 4 0 0 3 4 321 4 4 3 1 0 4 4 422 4 4 4 0 2 3 4 423 4 4 3 0 0 3 4 424 -- 4 3 2 0 0 0 225 4 4 2 0 0 3 4 426 3 4 2 4 0 3 4 427 4 4 3 1 0 4 4 428 4 4 2 0 0 4 -- --29 -- 4 3 0 0 3 4 430 -- 4 3 0 0 3 4 431 4 4 2 0 0 0 3 432 3 4 0 -- 0 2 4 434 4 3 4 2 0 4 435 4 4 0 0 3 4 440 3 4 2 0 1 0 4 443 4 4 0 0 2 4 444 4 3 4 1 0 4 445 4 4 -- 0 0 2 4 446 4 4 -- 1 0 3 4 451 4 4 -- 4 1 4 4 452 4 4 -- 0 3 2 4 453 4 4 -- 4 2 3 4 454 4 4 -- 3 2 2 4 455 4 4 -- 4 2 4 4 457 3 4 -- 0 0 0 0 058 4 4 -- 0 0 0 3 359 3 4 -- 1 0 0 3 360 4 4 -- 0 0 2 4 4__________________________________________________________________________COM- PIRI- PLASMO- PHTYO- CERCOSPORA VENTURIAPOUND PUCCINIA ERYSIPHE CULARIA PARA PHTHORA BOTRYTIS ARACHI- INAE-NUM- RECONDITA GRAMINIS ORYZAE VITICOLA INFESTANS CINEREA DICOLA QUALISBER (WHEAT) (BARLEY) (RICE) (VINE) (TOMATO) (GRAPE) (PEANUT) (APPLE)__________________________________________________________________________62 4 4 -- 0 0 3 4 464 3 4 -- 0 0 0 0 365 4 4 -- 0 0 4 3 466 4 4 -- 0 1 0 4 467 4 4 -- 0 0 2 4 469 4 4 -- 0 0 4 4 470 4 4 -- 0 0 4 4 471 3 4 0 0 3 4 472 4 4 -- 0 0 0 3 475 4 4 -- 3 0 2 4 481 4 3 -- 0 0 4 4 482 4 4 -- 0 0 4 4 483 4 4 -- 0 0 4 4 485 4 4 -- 1 0 3 4 486 4 4 -- 3 -- 4 4 487 4 4 -- 3 -- 4 4 489 4 4 -- 3 0 3 4 490 4 4 -- 0 0 3 4 391 4 4 -- 0 0 4 4 497 3 4 -- 0 -- 2 4 4102 4 4 -- 1 -- 4 3 4103 4 4 -- 0 0 4 4 4104 4 4 -- 0 0 0 3 4105 4 4 -- 0 0 0 4 4107 4 4 -- 1 0 0 4 4108 4 4 -- 0 0 4 4 4109 4 4 -- 3 0 1 4 4110 4 4 0 0 4 4 4111 4 4 -- 2 -- 0 2 4112 4 4 -- 3 -- 0 0 4117 4 4 -- 0 -- 0 1 4118 4 4 -- 4 -- 0 4 4121 4 4 -- 1 1 0 4 4122 0 4 -- 0 0 0 2 2123 0 4 -- 3 1 0 1 2125 4 4 -- 3 -- 0 3 4128 4 3 -- 1 0 -- 4 4129 4 4 -- 0 0 4 4 4130 4 4 -- 1 0 3 4 4131 4 4 -- 0 0 0 2 2132 4 4 -- 0 -- 0 3 4133 4 4 -- 0 -- -- 3 4139 4 4 -- 0 0 0 4 4140 4 4 -- 0 0 4 3 4142 4 3 -- 0 0 1 4 3147 4 4 -- 3 0 0 4 4167 4 4 -- 0 0 1 4 4168 4 4 -- -- -- 0 3 4176 4 4 -- 0 0 0 4 4177 4 4 -- 4 0 1 4 4178 4 4 -- 0 4 4 4179 4 4 -- 2 0 4 4 4195 4 4 -- 2 0 4 4 4196 4 4 -- 0 0 4 4 4198 4 4 -- 3 -- 0 4 4204 4 4 -- 0 -- 0 4 4228 4 4 -- 1 2 3 4235 4 -- 0 4 4 4236 4 4 -- 0 0 4 4 4244 4 4 -- 1 0 3 4 4248 4 4 -- 3 3 4 3 4250 2 4 -- 0 0 0 1 0251 4 4 -- 0 0 2 4 4252 4 4 -- 0 0 4 4 4253 4 -- 0 0 4 4 4254 4 4 -- 0 0 2 4 4255 4 3 -- 0 0 1 3 3256 4 4 -- 0 0 2 4 4257 4 4 -- 0 0 3 4 4258 4 4 -- 2 4 4 4259 4 4 -- 0 -- 3 4 4260 3 4 -- 3 -- 2 4 4261 3 4 -- 1 -- 4 4 4262 4 4 -- 0 -- 4 4 3263 4 4 -- 0 0 2 4 4264 4 4 -- 2 -- 1 4 3265 3 4 -- 0 1 1 0266 4 4 -- 0 -- 0 -- 4267 4 4 -- 0 -- 4 -- 4268 4 4 -- 0 -- 4 -- 4269 4 4 -- 0 0 4 4 4270 4 4 -- 4 3 4 4 4271 4 4 -- 4 0 4 4 4272 3 4 -- 0 0 0 4 3273 4 4 -- 0 0 3 3 4274 3 4 -- 2 0 2 0 4275 4 4 -- 0 -- 0 4 4276 4 4 -- 3 0 4 4 4277 4 4 -- 3 -- -- 4 4279 4 4 -- 2 -- 0 3 4280 4 4 -- 2 0 3 3 3281 3 4 -- 3 -- 0 4 4282 4 4 -- 3 -- -- 3 4284 4 4 -- 0 0 1 4 4285 4 4 -- 1 0 4 3 4286 1 4 -- 0 1 0 0 0287 3 4 -- 0 0 0 0 0288 4 4 -- 0 -- 0 4 4289 4 4 -- 0 -- 0 3 4290 4 4 -- 0 -- 0 1 4291 4 4 -- 1 -- 0 1 4292 4 4 -- 3 -- 0 4 4293 4 4 -- 0 -- -- 4 4294 4 4 -- 0 -- 0 4 4295 4 4 -- 0 -- 0 3 3296 4 4 -- 0 -- 0 4 4297 4 4 -- 2 -- 0 4 4301 4 4 -- 0 -- 0 4 4302 4 4 -- 0 -- -- 2 3303 0 3 -- 1 -- -- 0 0__________________________________________________________________________
EXAMPLE 21
This Example illustrates the plant growth regulating properties of the compounds. The compounds were applied in the form of a 4000 ppm solution in distilled water and the solution was then applied to the foliage of young seedlings of various plants. The experiments were replicated twice. After 12 or 13 days from treatment the plants were assessed for plant growth regulating effects and phytotoxic symptoms.
Table III shows the stunting effect of the compounds on the vegetative growth using the following grading:
1=0-30% retardation
2=31-75% retardation
3=75% retardation
If no figure is given, the compound was substantially inactive as a stunting agent. Additional plant growth regulating properties are indicated as follows:
G=darker green lead colour
A=apical effect
T=tillering effect.
TABLE III__________________________________________________________________________COM-POUNDNUM- SUGAR AGROSTIS CYNODON DACTYLIS TO- -BER SOYA COTTON 7BEET TENUIS DAC TYLON GLOMERATA WHEAT BARLEY MAI ZE MATO__________________________________________________________________________ 1 3G 2G 1 G 2 1 2G 1 1 2 1G 6 1 3G 3 2G 2G 1G 3G 9 2G G 1 1G 1G 1G 1T 2G11 2G 1G 3G 3G 3G 3G 3G12 1 3G 2G 1G 1 2 T 3G13 1G 2 1G 1GT 2 214 1G 2G 1G 1G 1G 1 2 3G15 2G 3G 1 2 1 1 2GA17 G 2 2G G18 3 2G 2G 1 1 1 2 3G19 2G 2 2GT 2 1 1 3GA20 2G 2G 2G 2 2 2 1 1 3GA21 2G 2G 2G 2G 2G 2G 1 1 1 3A23 1 2 1G 1 1 1 2GA25 2G 3G 3GA 1 1 T 3 2G26 G 2G 1G 3 327 1G 2G 1 3G28 2G 1 2G31 3GA 2G 1G T 1 3 3G32 2G 2 3G 3G 1 1 1 1 3GA34 2GA 1G 2G 2G 2G 2G 3 3GA35 2G 2G 3GA 3G 3G 2G 1 1 2 3G41 1G 1G 1G 1 1 242 1G 1G44 1GA G 3G 1G T 1 3GA46 2GA G 2G 1T 2GAT49 2G 1G 1 1GT 1GT 2G50 1 2G 2G 1G52 1 T 153 1G 3G T 1 2G54 G 1G 2G T 2 3G55 1G 3G 3G 1 1 3A69 G70 1G71 1G 1G 1G 1 1 2G75 1G G 1GT81 YG 1 2G85 2GA 3GA 2G 3GT89 2G 2G 1 1 1G 1G90 1G 2G 1G 1 2 1 1 1G 1G104 1T 1105 1G 1G 1107 2G 1 1G108 3GA 1 2G109 3G 3G128 2G 2G 2G 2G 2G 1G 3GA129 3G 2G 2GAT 3G 3G 2G 1T 1 3G147 2 1 1 2177 2G 1 1 2196 2G 3G 3G 1 1G 1G 1 3GA248 2G 2G 3G 3G 2G 2G 3G 1G 3GA250 G251 1G 2G 2G 1 2GA252 1GT 1GA 3GA 2 2GT__________________________________________________________________________
Claims
  • 1. A compound of formula (1) ##STR13## wherein R.sup.1 is C.sub.1 -C.sub.6 alkyl, halophenyl, cyclobutyl, cyclopropyl or cyclopentyl and R.sup.2 is halophenyl or halophenyl substituted by C.sub.1 -C.sub.6 alkyl or C.sub.1 -C.sub.5 alkoxy, in the form of an ether which is a C.sub.1-6 alkyl ether, a C.sub.3-4 alkenyl ether or a benzyl ether wherein the benzyl is unsubstituted or substituted with chlorine, or in the form of an ester which is an alkanoyl, alkenoyl or alkynoyl, each of 1 to 4 carbons, or benzoyl or halo- or nitro-substituted benzoyl ester thereof.
  • 2. A compound of formula (1): ##STR14## wherein R.sup.1 is C.sub.1 -C.sub.6 alkyl, R.sup.2 is halophenyl and R.sup.11 is C.sub.1 -C.sub.6 alkyl.
  • 3. An ether or ester according to claim 1 wherein R.sup.1 and R.sup.2 are both halophenyl.
  • 4. An ether or ester according to claim 1 wherein R.sup.1 and R.sup.2, which may be the same or different, are each chlorophenyl or fluorophenyl.
  • 5. An ether or ester according to claim 1 of the compound 1-(1,2,4-triazol-1-yl)-2-(4-fluorophenyl)-2-(4-chlorophenyl)ethan-2-ol.
  • 6. An ether or ester according to claim 1 of the compound 1-(1,2,4-triazol-1-yl)-2-(2-fluorophenyl)-2-(4-fluorophenyl)ethan-2-ol.
  • 7. An ether or ester according to claim 1 of the compound 1-(1,2,4-Triazol-1-yl)-2-(4-fluorophenyl)-2-(2,4-dichlorophenyl)ethan-2-ol
  • 8. An ether or ester selected from the ethers and esters of the compounds
  • 1-(1,2,4-Triazol-1-yl)-2,2-di(4-fluorophenyl)ethan-2-ol,
  • 1-(1,2,4-Triazol-1-yl)-2-(4-chlorophenyl)-2-(2-chlorophenyl)ethan-2-ol.
  • 1-(1,2,4-Triazol-1-yl)-2-(4-fluorophenyl)-2-(2-chlorophenyl)ethan-1-ol.
  • 1-(1,2,4-Triazol-1-yl)-2-(2-chloro-4-methoxyphenyl)-2-(4-fluorophenyl)ethan-2-ol.
  • 1-(1,2,4-Triazol-1-yl)-2-(4-fluorophenyl)-2-(2-fluoro-4-methyl-phenyl)ethan-2-ol, or
  • 1-(1,2,4-Triazol-1-yl)-2-(4-fluorophenyl)-2-(2-chloro-4-methyl-phenyl)ethan-2-ol.
  • 9. C.sub.1-4 alkyl ethers and acetyl esters of compounds according to claim 1.
  • 10. A fungicidal composition characterized in that it comprises, as an active ingredient, an effective amount of ether or ester as defined in claim 1, together with a carrier or diluent.
  • 11. A method of combating fungi, especially fungal diseases in a plant, which method comprises applying to the plant, to seed of the plant or to the locus of the plant or seed an effective amount of ether or ester according to claim 1.
  • 12. A plant growth regulating composition characterized in that it comprises, as an active ingredient, an effective amount of ether or ester as defined in claim 1, together with a carrier therefore.
Priority Claims (4)
Number Date Country Kind
7908003 Mar 1979 GBX
7932819 Sep 1979 GBX
8005141 Feb 1980 GBX
8026884 Aug 1980 GBX
Parent Case Info

This application is a continuation of Ser. No. 907,180, filed Sept. 16, 1986, now abandoned, which is itself a continuation of Ser. No. 593,271, filed Mar. 26, 1984, now abandoned, which is itself a continuation of Ser. No. 293, 338, filed Aug. 17, 1981, now abandoned, which is a continuation-in-part of Ser. No. 183,140, filed Sept. 3, 1980, now U.S. Pat. No. 4,551,469, which itself is a continuation-in-part of Ser. No. 124,253, filed Feb. 25, 1980, now U.S. Pat. No. 4,654,332.

US Referenced Citations (6)
Number Name Date Kind
4243405 Balassubramanyon et al. Jan 1981
4301166 Regel et al. Nov 1981
4315016 Balassubramanyan et al. Feb 1982
4414210 Miller et al. Nov 1983
4472415 Worthington et al. Sep 1984
4620011 Worthington et al. Oct 1986
Foreign Referenced Citations (11)
Number Date Country
0015756 Sep 1980 EPX
0017080 Oct 1980 EPX
0011768 Nov 1980 EPX
0011769 Nov 1980 EPX
0019189 Nov 1980 EPX
0036153 Sep 1981 EPX
2431407 Jan 1976 DEX
2623129 Nov 1977 DEX
7613372 Jun 1977 NLX
1563199 Mar 1980 GBX
2064520 Jun 1981 GBX
Continuations (3)
Number Date Country
Parent 907180 Sep 1986
Parent 593271 Mar 1984
Parent 293338 Aug 1981
Continuation in Parts (2)
Number Date Country
Parent 183410 Sep 1980
Parent 124253 Feb 1980