CA2245541A1 - Substituted 2-phenylpyridines - Google Patents

Abstract

The invention concerns substituted 2-phenylpyridines of formula (I) and their salts, in which X = a bond, 1,2-ethinediyl, an optionally substituted methylene-, 1,2-ethanediyl- or 1,3-propylene bridge, optionally substituted methyleneoxymethylene, methylenethiamethylene, ethene-1,2-diyl, optionally substituted oxymethylene, thiamethylene, oxyethylene or thiaethylene bonded to the phenyl ring via the heteroatom; Y = -O-, -S-; -Z1 = -O-, -S-, -N(R7)-; Z2 = -O2-, -S-, -N(R8)-; R1, R2, R7, R8 = H, C1-C6-alkyl, C1-C6-alkyl halide, hydroxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4alkoxy-C1-C4alkyl, C1-C4alkoxy halide-C1-C4-alkyl, C3-C4-alkenyloxy-C1-C4-alkyl, C3-C4-alkinyloxy-C1-C4-alkyl, C3-C8-cycloalkoxy-C1-C4-alkyl, amino-C1-C4-alkyl, C1-C4-alkylamino-C1-C4-alkyl, di-(C1-C4-alkyl)amino-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-alkylthiohalide-C1-C4-alkyl, C3-C4-alkenylthio-C1-C4-alkyl, C3-C4alkinylthio-C1-C4-alkyl, C1-C4-alkylsulphinyl-C1-C4-alkyl, C1-C4-alkylsulphinylhalide-C1-C4-alkyl, C3-C4-alkenylsulphinyl-C1-C4-alkyl, C3-C4-alkinylsulphinyl-C1-C4-alkyl, C1-C4-alkylsulphonyl-C1-C4-alkyl, C1-C4-alkylsulphonyl halide-C1-C4-alkyl, C3-C4-alkenylsulphonyl-C1-C4-alkyl, C3-C4-alkinylsulphonyl-C1-C4-alkyl, C3-C6-alkenyl, C3-C6-alkenyl halide, cyano-C3-C6-alkenyl, C3-C6-alkinyl, C3-C6-alkinyl halide, cyano-C3-C6-alkinyl, hydroxycarbonyl-C1-C4-alkyl, (C1-C4-alkoxy)-carbonyl-C1-C4-alkyl, (C1-C4-alkylthio)carbonyl-C1-C4-alkyl, amino-carbonyl-C1-C4-alkyl, (C1-C4-alkyl)aminocarbonyl-C1-C4-alkyl, di-(C1-C4-alkyl)aminocarbonyl-C1-C4-alkyl, optionally substituted C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, phenyl, phenyl-C1-C4-alkyl, 3- to 7-members heterocyclyl or heterocyclyl-C1-C4-alkyl, wherein all the heterocycles can contain a (thio)carbonyl ring member, or R1 +
R2 and/or R1 + R7 and/or R2 + R8 together in each case are an optionally substituted 1,2-ethanediyl-, 1,3-propylene-, tetramethylene-, pentamethylene-or ethyleneoxyethylene chain; or R1 + R2 together are optionally substituted 1,2-phenylene; R3 = CN, halogen, C1-C4-alkyl, C1-C4 alkyl halide, C1-C4 alkoxy or C1-C4 halkoxy halide; R4, R5 are H, halogen; R6 is halogen, C1-C4 alkyl halide; and n = 0,1. The invention further concerns the use of these substances as herbicides and for desiccating/defoliating plants.

Description

0050/46587 CA 0224~4l l998-08-06 Substituted 2-phenylpyridines The present invention relates to novel substituted 2-phenyl-5 pyridines of the formula I

0 R~N ~ X ~ z2R2 R6 (~) zlRl where the variables have the following me~n;ngs:
X is a chemical bond, 1,2-ethynediyl or - a methylene, 1,2-ethanediyl or 1,3-propylene bridge, which, if desired, can have attached to it a hydroxyl, amino or C1-C4-alkylamino substituent;
- methyleneoxymethylene, methylenethiamethylene, ethene-1,2-diyl or - oxymethylene, thiamethylene, oxyethylene or thiaethylene, bonded to the phenyl ring via the hetero atom, it being possible, if desired, for the last two ch~;n.~ to have a hydroxyl, amino or C1-C4-alkylamino group attached to the carbon atom adjacent to the phosphorous;
and it being possible for each of the last-mentioned 10 bridges to have attached to it one or two of the following substituents: cyano, carboxyl, halogen, Cl-C4-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-haloalkoxy, (C1-C4-alkoxy)carbonyl and/or di-(Cl-C4-alkyl)amino;
.
Y is oxygen or sulfur;
35 zl is oxygen, sulfur or -N(R7)-;
z2 iS oxygen, sulfur or -N(R8)-;
Rl~ R2, R7 and R8 independently of one another are 40 hydrogen, Cl-C6-alkyl, Cl-C6-haloalkyl, hydroxy-Cl-C4-alkyl, cyano-Cl-C4-alkyl, Cl-C4-alkoxy-Cl-C4-alkyl, Cl-C4-haloalkoxy-Cl-C4-alkyl, C3-C4-alkenyloxy-Cl-C4-alkyl, C3-C4-alkynyloxy-Cl-C4-alkyl, C3-C8-cycloalkoxy-Cl-C4-alkyl, amino-Cl-C4-alkyl, Cl-C4-alkylamino-Cl-C4-alkyl, di(Cl-C4-alkyl)amino-Cl-C4-alkyl, Cl-C4-alkylthio-45 Cl-C4-alkyl, C1-C4-haloalkylthio-C1-C4-alkyl, C3-C4-alkenylthio-Cl-C4-alkyl, C3-C4-alkynylthio-C1-C4-alkyl, Cl-C4-alkylsulfinyl-Cl-Cq,-alkyl, Cl-C4-haloalkylsulfinyl-Cl-C4-alkyl, C3-C4-alkenylsul--~ 0050/46587 CA 0224~4l l998-08-06 finyl-C1-C4-alkyl, C3-C4-alkynylsulfinyl-C1-C4-alkyl, Cl-C4-alkyl-sulfonyl-Cl-C4-alkyl, Cl-C4-haloalkylsulfonyl-Cl-C4-alkyl, C3-C4-alkenylsulfonyl-C1-C4-alkyl, C3-C4-alkynylsulfonyl-Cl-C4-alkyl, C3-C6-alkenyl, C3-C6-haloalkenyl, cyano-C3-C6-alkenyl, 5 C3-C6-alkynyl, C3-C6-haloalkynyl, cyano-C3-C6-alkynyl, hydroxycar-bonyl-Cl-C4-alkyl, (Cl-C4-alkoxy)carbonyl-Cl-C4-alkyl, (Cl-C4-alkylthio)carbonyl-Cl-C4-alkyl, aminocarbonyl-Cl-C4-alkyl, - (C1-C4-alkyl)aminocarbonyl-C1-C4-alkyl, di(C1-C4-alkyl)aminocar-bonyl -Cl -C4 -alkyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, phenyl, phenyl-C1-C4-alkyl or 3- to 7-membered heterocyclyl or heterocyclyl-C1-C4-alkyl, it being possible, if desired, for all heterocycles to contain a 15 carbonyl or thiocarbonyl ring member, and it being possible for all cycloalkyl, phenyl and heterocyclyl rings to be unsubstituted or to have attached to them one to four substituents, in each case selected from the group consisting of 20 halogen, cyano, nitro, amino, hydroxyl, carboxyl, C1-C4-alkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-haloalkoxy, Cl-cg-alkylthio, Cl-C4-haloalkylthio, Cl-C4-alkylsulfonyl, Cl-C4-haloaikylsulfonyl, (C1-C4-alkyl)carbonyl, (C1-C4-haloalkyl)carbonyl, (C1-C4-alkoxy)carbonyl, (C1-C4-alkyl)carbonyloxy, (C1-C4-halo-25 alkyl)carbonyloxy and di(C1-C4-alkyl)amino, or R1 and R2 or R1 and R7 and/or R2 and R8 in each case together form a 1,2-ethanediyl, 1,3-propylene, tetramethylene, pentamethylene 30 or ethyleneoxyethylene chain which, if desired, can be substi-tuted by one to four C1-C4-alkyl and/or one or two (C1-C4-alkoxy)carbonyl groups, or 35 R1 and R2 together are 1,2-phenylene which can be unsubstituted or have attached to it one to three substituents, in -each case selected from the group consisting of cyano, nitro, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and Cl-Cg-halOalkoxy;
R3 is cyano, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
R4, R5 in each case are hydrogen or halogen;
R6 is halogen or C1-C4-haloalkyl;

0050/46587 CA 0224~4l l998-08-06 n i8 zero or one;
and to the agriculturally useful salts of the compounds I.
5 Furt~r~re, the invention relates to - the use of the compounds I as herbicides or for the desicca-tion/defoliation of plants, - herbicidal compositions and compositions for the desiccation/
defoliation of plants which comprise the compounds I as active substances, - processes for the preparation of the compounds I and of her-bicidal compositions and compositions for the desiccation/
defoliation of plants which make use of the compounds I, and - methods of controlling undesirable vegetation and for the desiccation/defoliation of plants using the compounds I.
US 5,434,288 describes certain benzene derivatives as phospholi-pase A2 inhibitors. The broad definition of these compounds also includes some of the present substituted 2-phenylpyridines I if 20 the suitable substituents are selected.
Furt~rmore, some of the compounds I - when suitable substituents are chosen - come under the general formulae of - platelet-activating factor (PAF) antagonists described in Gs-A 2 263 109;
- supported catalysts for the production of acetic acid which are described in DE-A 41 21 959;
- antithrombic, antiaggregatory and tumor-inhibitory reactive substances described in EP-A 537 696;
30 - intermediates for the preparation of certain NMDA receptor inhibitors, mentioned in EP-A 421 436;
- int~rme~;~tes for the preparation of certain insecticides, mentioned in EP-A 544 587;
- interm~;ates for the preparation of certain PDE IV inhibi-tors, mentioned in WO 95/35281;
- intermediates for the preparation of asymmetric 9-cyano-styryl-10-styrylanthracene derivatives, mentioned in JP-A 05/178 810;
- int~rm~;ates for the preparation of certain insecticides, acaricides, nematicides and fungicides, mentioned in EP-A 474 042.

2-Phenylpyridines as herbicides or for the desiccation/defoli-ation of plants have already been taught in WO 95/02580.
However, the herbicidal properties of the prior-art 2-phenylpyri-dines with regard to the harmful plants are not always entirely 0050/46587 CA 0224~541 1998-08-06 satis~actory.
It is an object o~ the present invention to provide novel herbi-cidally active 2-phenylpyridines which allow better targeted con-5 trol of undesirable plants than has been possible to date. Theobject also extends to the provision of novel compounds which act as desiccants/defoliants.
We have found that this ob~ect is achieved by the present substi-10 tuted 2-phenylpyridines of the formula I and by their herbicidal activity.
Fur~h~rmore, there have been found herbicidal compositions which comprise the compounds I and which have a very good herbicidal 15 activity. Moreover, there have been found processes for the preparation of these compositions and methods of controlling un-desirable vegetation usin~ the compounds I.
In addition, we have found that the compounds I are also suitable ao for the desiccation/defoliation of parts of plants, suitable plants being crop plants such as cotton, potatoes, oilseed rape, sunflowers, soybeans or field beans, in particular cotton. Thus, we have found compositions for the desiccation and/or defoliation of plants, processes for the preparation of these compositions 25 and methods for the desiccation andlor defoliation of plants U5-ing the compounds I.
DepPn~; ng on the substitution pattern, the compounds of the for-mula I can contain one or more chiral centers, in which case they 30 are present in the form of enantiomer or diastereomer mixtures.
E/Z isomers are also possible, depending on the m~n; ng of X. The invention relates both to the pure enantiomers or diastereomers and to mixtures of these.
35 Agriculturally useful salts are to be understood mainly as the salts of I with those cations, and acid addition salts of I with those acids, which do not adversely affect the herbicidal or des-iccant/defoliant action of I.
40 Thus, suitable cations are, in particular, the ions of the alkali metals, preferably sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and the ammonium ion, which can have attached to it a C1-C4-alkyl, 45 phenyl or benzyl substituent and, if desired, additionally one to three further C1-C4-alkyl radicals, preferably diisopropylammo-nium, tetramethyl~mmnn;um, tetrabutyl~mmo~;um, trimethylbenzyl-0050/46587 CA 02245541 l998-08-06 ~ o~;um, furt~rmore phosphonium ions, preferably tri-(Cl-C4-alkyl)phosphonium, sulfonium ions, preferably tri(Cl-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Cl-C4-alkyl)sulfoxonium.

Anions of useful acid addition salts are mainly fluoride, chlo-ride, bromide, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, car-bonate, hexafluorosilicate, hexafluorophosphate, benzoate, oxa-10 late, dodecylbenzenesulfonate, and the anions of Cl-c4-~lk~noic acids, preferably formate, acetate, propionate and butyrate.
The organic moieties mentioned for the substituents Rl to R3 an~
R6 to R8 or as radicals on X represent collective terms for indi-15 vidual enumerations of the individual group members. All carbonc~;n~, i.e. all alkyl, haloalkyl, hydroxyalkyl, cy~no~lkyl, ami-noalkyl, hydroxycarbonylalkyl, aminocarbonylalkyl, alkoxy, - haloalkoxy, alkylthio, haloalkylthio, alkylsulfinyl, halosulfi-nyl, alkylsulfonyl, haloalkylsulfonyl, alkylamino, dialkyl ~m~ no, 20 alkenyl, haloalkenyl, cyanoalkenyl, alkenyloxy, alkenylthio, al-kenylsulfinyl, alkenylsul~onyl, alkynyl, haloalkynyl, cy~no~lky-nyl, alkynyloxy, alkynylthio, alkynylsulfinyl, alkynylsulfonyl moieties, can be straight-chain or branched. Halogenated substi-tuents preferably have attached to them one to five identical or 25 different halogen atoms.
The me~n;ng of halogen is in each case fluorine, bromine, chlo-rine or iodine, in particular fluorine or chlorine.
30 Other examples of me~n;ngs are:
- C1-C4-alkyl: methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1,1-dimethylethyl, in par-ticular methyl or ethyl;
- Cl-C4-haloalkyl: a C1-C4-alkyl radical as mentioned above - which is partially or fully substituted by fluorine, chlo-rine, bromine and/or iodine, i.e., for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluorome-thyl, trifluoromethyl, chlorofluoromethyl, dichlorofluorome-thyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-tri-fluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoro-ethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pen-tafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoro-propyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-tri-fluoropropyl, 3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoro-propyl, hepta~luoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloromethyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobu-tyl, in particular chloromethyl, ~luoromethyl, difluorome-thyl, trifluoromethyl, 2-fluoroethyl, Z-chloroethyl or 2,2,2-trifluoroethyl;
- Cl-C6-alkyl: Cl-C4-alkyl as mentioned abo~e and also, for example, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methyl-butyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-di-methylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methyl-pentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, Z,2-dimethylbutyl, 2,3-~imethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethyl-butyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl, in particu-lar methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1,1-di-methylethyl, n-pentyl or n-hexyl;
~0 - C1-C6-haloalkyl: a Cl-C6-alkyl radical as mentione~ abo~e which is partially or fully substituted by fluorine, chlorine, bromine andlor iodine, i.e., ~or example, one of the radical~ mentioned under C1-C4-haloalkyl, or 5-~luoro-1-pentyl, 5-chloro-1-pentyl, 5-bromo-1-pentyl, 5-iodo-1-pentyl, 5,5,5-trichloro-1-pentyl, lln~c~fluoro-pentyl, 6-~luoro-1-hexyl, 6-chloro-1-hexyl, 6-bromo-1-hexyl, 6-iodo-1-hexyl, 6,6,6-trichloro-1-hexyl or dodecafluorohexyl, in particular chloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, 2-fluoroethyl, 2-chloroethyl or 2,2,2-tri-~luoroethyl;
- hydroxy-C1-C4-alkyl: for example hydroxymethyl, 2-hy~roxy-eth-1-yl, 2-hy~roxyprop-1-yl, 3-hydroxyprop-1-yl, 1-hydroxy-prop-2-yl, 2-hydroxybut-1-yl, 3-hydroxybut-1-yl, 4-hydroxy-but-1-yl, 1-hydroxybut-2-yl, 1-hydroxybut-3-yl, 2-hydroxy-~ut-3-yl, 1-hy~roxy-2-methylprop-3-yl, 2-hydroxy-2-methyl-prop-3-yl or 2-hydroxymethylprop-2-yl, in particular 2-hydroxyethyl;
~ 40 - cyano-Cl-C4-alkyl: cyanomethyl, 1-cyanoeth-1-yl, 2-cyano-eth-1-yl, l-cyanoprop-1-yl, 2-cyanoprop-1-yl, 3-cyano-prop-1-yl, 1-cyanoprop-2-yl, 2-cyanoprop-2-yl, 1-cyano-but-1-yl, 2-cyanobut-1-yl, 3-cyanobut-1-yl, 4-cyanobut-1-yl, 1-cyanobut-2-yl, 2-cyanobut-2-yl, 1-cyanobut-3-yl, 2-cyano-but-3-yl, 1-cyano-2-methylprop-3-yl, 2-cyano-2-methyl-prop-3-yl, 3-cyano-2-methylprop-3-yl or 2-cyanomethyl-_ ~ 0050/46587 CA 0224~541 1998-08-06 prop-2-yl, in particular cyanomethyl or 2-cyanoethyl;
- amino-C1-C4-alkyl: ~or example aminomethyl, 2-aminoethyl, 2-aminoprop-1-yl, 3-aminoprop-1-yl, 2-A~inobut-1-yl, 3-amino-but-1-yl, 4 - ~mi nohut-1-yl, 1-Am;nobut-2-yl, 3 -~m; nohut - 2 - yl, 4-~m;nohut-2-yl, 1-(aminomethyl)eth-1-yl, 1-(~m;n~m~thyl)-1-~methyl)eth-1-yl or 1- (~m; no~thyl)prop-l-yl~ in particular ~m~nomethyl or 2-aminoethyl;
10 - hydroxycarbonyl-C1-C4-alkyl: hydroxycarbonylmethyl, 1-(hydrox-ycarbonyl)ethyl, 2-(hydroxycarbonyl)ethyl, 1-(hydroxycarbo-nyl)prop-1-yl, 2-(hydroxycarbonyl)prop-1-yl, 3-(hydroxycarbo-nyl)prop-l-yl, 1-(hydroxycarbonyl)but-1-yl, 2-(hydroxycarbo-nyl)but-1-yl, 3-(hydroxycarbonyl)but-1-yl, 4-(hydroxycarbo-nyl)but-1-yl, 1-(hydroxycarbonyl)but-2-yl, 2-(hydroxycarbo-nyl)but-2-yl, 3-(hydroxycarbonyl)but-2-yl, 4-(hydroxycarbo-nyl)but-2-yl, 1-(hydroxycarbonylmethyl)eth-1-yl, 1-(hydroxy-carbonylmethyl)-1-(methyl)eth-1-yl or 1-(hydroxycarbonyl-methyl)prop-1-yl, in particular hydroxycarbonylmethyl or 2-(hydroxycarbonyl)ethyl;
- aminocarbonyl-Cl-C4-alkyl: aminocarbonylmethyl, 1-(aminocarbo-nyl)ethyl, 2-(aminocarbonyl)ethyl, l-(aminocarbonyl)prop-l-yl, 2-(aminocarbonyl)prop-1-yl, 3-(aminocarbonyl)prop-1-yl, 1-(aminocarbonyl)but-1-yl, 2-(aminocarbonyl)but-1-yl, 3-(ami-nocarbonyl)but-l-yl, 4-(aminocarbonyl)but-1-yl, l-(aminocar-bonyl)but-2-yl, 2-(aminocarbonyl)but-2-yl, 3-(aminocarbo-nyl)but-2-yl, 4-(aminocarbonyl)but-2-yl, 1-(aminocarbonyl-methyl)eth-l-yl, l-(aminocarbonylmethyl)-l-(methyl)eth-l-yl or 1-(aminocarbonylmethyl)prop-1-yl, in particular aminocar-bonylmethyl or 2-(aminocarbonyl)ethyl;
- phenyl-Cl-C~-alkyl: benzyl, 1-phenylethyl, 2-phenylethyl, ~ l-phenylprop-l-yl, 2-phenylprop-1-yl, 3-phenylprop-1-yl, l-phenylbut-1-yl, 2-phenylbut-1-yl, 3-phenylbut-1-yl, 4-phe-nylbut-1-yl, 1-phenylbut-2-yl, 2-phenylbut-2-yl, 3-phenyl-but-2-yl, 4-phenylbut-2-yl, 1-(phenylmethyl)eth-1-yl, l-(phe-nylmethyl)-1-(methyl)eth-1-yl or l-(phenylmethyl)prop-l-yl, in particular benzyl or 2-phenylethyl;
- heterocyclyl-c1-C4-alkyl: heterocyclylmethyl, l-heterocyclyl-ethyl, 2-heterocyclylethyl, 1-heterocyclylprop-1-yl, 2-he-terocyclylprop-l-yl, 3-heterocyclylprop-1-yl, 1-heterocyclyl-but-1-yl, 2-heterocyclylbut-1-yl, 3-heterocyclylbut-1-yl, 4-heterocyclylbut-1-yl, 1-heterocyclylbut-2-yl, 2-heterocy-clylbut-2-yl, 3-heterocyclylbut-2-yl, 4-heterocyclylbut-2-yl, 1-(heterocyclylmethyl)eth-1-yl, l-(heterocyclylmethyl)-~ 0050/46587 CA 0224s~4l l998-08-06 1-(methyl)eth-1-yl or 1-(heterocyclylmethyl)prop-1-yl, in particular heterocyclylmethyl, 2-heterocyclylethyl or 3-het-erocyclylpropyl; 3-oxetanylmethyl, 2-(1,3-oxazolin-2-on-3-yl)ethyl and 3-(2-pyridyl)propyl are especially preferred;
- (C1-C4-alkyl)carbonyl: CO-CH3, C0-C2H5, n-propylcarbonyl, 1-methylethylcarbonyl, n-butylcarbonyl, CO-CH(CH3)2, 2-methyl-propylcarbonyl or CO-C(CH3)3, in particular CO-CH3;
10 - (C1-C4-haloalkyl)carbonyl: a (Cl-C~-alkyl)carbonyl radical as mentioned above which is partially or fully substituted by fluorine, chlorine, bromine and/or iodine, i.e., for example, chloroacetyl, dichloroacetyl, trichloroacetyl, ~luoroacetyl, difluoroacetyl, trifluoroacetyl, chlorofluoroacetyl, dichlo-rofluoroacetyl, chlorodifluoroacetyl, 2-fluoroethylcarbonyl, 2-chloroethylcarbonyl, 2-bromoethylcarbonyl, 2-iodoethylcar-bonyl, 2,2-difluoroethylcarbonyl, 2,2,2-trifluoroethylcarbo-nyl, 2-chloro-2-fluoroethylcarbonyl, 2-chloro-2,2-difluoro-ethylcarbonyl, 2,2-dichloro-2-fluoroethylcarbonyl, 2,2,2-trichloroethylcarbonyl, CO-C2F5, 2-fluoropropylcarbonyl, 3-fluoropropylcarbonyl, 2,2-difluoropropylcarbonyl, 2,3-di-fluoropropylcarbonyl, 2-chloropropylcarbonyl, 3-chloropropyl-carbonyl, 2,3-dichloropropylcarbonyl, 2-bromopropylcarbonyl, 3-bromopropylcarbonyl, 3,3,3-trifluoropropylcarbonyl, 3,3,3-trichloropropylcarbonyl, 2,2,3,3,3-pentafluoropropyl-carbonyl, heptafluoropropylcarbonyl, 1-~fluoromethyl)-2-fluo-roethylcarbonyl, 1-(chloromethyl)-2-chloroethylcarbonyl, 1-(bromomethyl)-2-bromoethylcarbonyl, 4-fluorobutylcarbonyl, 4-chlorobutylcarbonyl, 4-bromobutylcarbonyl or nonafluorobu-tylcarbonyl, in particular trifluoroacetyl;
- (C1-C4-alkyl)carbonyloxy: acetyloxy, ethylcarbonyloxy, n-pro-pylcarbonyloxy, 1-methylethylcarbonyloxy, n-butylcarbonyloxy, 1-methylpropylcarbonyloxy, 2-methylpropylcarbonyloxy or 1,1-dimethylethylcarbonyloxy, in particular acetyloxy;
- (C1-C4-haloalkyl)carbonyloxy: a (Cl-C4-alkyl)carbonyloxy radi-cal as mentioned above which is partially or fully substi-tuted by fluorine, chlorine, bromine and/or iodine, i.e., for example, chloroacetyloxy, dichloroacetyloxy, trichloroacety-loxy, fluoroacetyloxy, difluoroacetyloxy, trifluoroacetyloxy, chlorofluoroacetyloxy, dichlorofluoroacetyloxy, chlorodifluo-roacetyloxy, 2-fluoroethylcarbonyloxy, 2-chloroethylcarbony-loxy, 2-bromoethylcarbonyloxy, 2-iodoethylcarbonyloxy, 2,2-difluoroethylcarbonyloxy, 2,2,2-trifluoroethylcarbonyl-oxy, 2-chloro-2-fluoroethylcarbonyloxy, 2-chloro-2,2-difluo-roethylcarbonyloxy, 2,2-dichloro-2-fluoroethylcarbonyloxy, 0050/46587 CA 0224~541 1998-08-06 2,2,2-trichloroethylcarbonyloxy, pentafluoroethylcarbonyloxy, 2-fluoropropylcarbonyloxy,3-fluoropropylcarbonyloxy, 2,2-di-fluoropropylcarbonyloxy, 2,3-difluoropropylcarbonyloxy, 2-chloropropylcarbonyloxy, 3-chloropropylcarbonyloxy, 2,3-dichloropropylcarbonyloxy, 2-bromopropylcarbonyloxy, 3-bromopropylcarbonyloxy, 3,3,3-trifluoropropylcarbonyloxy, 3,3,3-trichloropropylcarbonyloxy, 2,2,3,3,3-penta~luoropro-pylcarbonyloxy, heptafluoropropylcarbonyloxy, l-~luoro-methyl)-2-fluoroethylcarbonyloxy, 1-(chloromethyl)-2-chloro-ethylcarbonyloxy, 1-(bromomethyl)-2-bromoethylcarbonyloxy, 4-fluorobutylcarbonyloxy, 4-chlorobutylcarbonyloxy, 4-bromo-butyl or nonafluorobutyl, in particular trifluoroacetoxy;
- C1-C4-alkoxy: methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, l-methylpropoxy, 2-methylpropoxy or 1,1-dimethyl-ethoxy, in particular methoxy or ethoxy;
- C1-C4-haloalkoxy: a C1-C4-alkoxy radical as mentioned above which i~ partially or fully substituted by fluorine, chlo-rine, bromine and/or iodine, i.e., for example, chloro-methoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, tri~luoromethoxy, chlorofluoromethoxy, dich-lorofluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoro-ethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-~luoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, OC2F5, 2-fluoropropoxy, 3-fluoropro-poxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy, 2-chloropro-poxy, 3-chloropropoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropro-poxy, 2,2,3,3,3-pentafluoropropoxy, heptafluoropropoxy, l-(fluoromethyl)-2-fluoroethoxy, 1-(chloromethyl)-2-chloro-~ ethoxy, 1-(bromomethyl)-2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy, in partic-ular 2-chloroethoxy or 2,2,2-trifluoroethoxy;
- (C1-C4-alkoxy)carbonyl: methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, 1-methylethoxycarbonyl, n-butoxycarbonyl, 1-methylpropoxycarbonyl, 2-methylpropoxycarbonyl or 1,1-dime-thylethoxycarbonyl, in particular methoxycarbonyl or ethoxy-carbonyl;
- Cl-C6-alkylthio: methylthio, ethylthio, n-propylthio, 1-methy-lethylthio, n-butylthio, l-methylpropylthio, 2-methylpropyl-thio or 1,1-dimethylethylthio, in particular methylthio or ethylthio;

0050/46587 CA 0224~541 l998-08-06 - Cl-C4-alkylamino: methylamino, ethyiamino, n-propyl~m~n~, l-methylethylamino, n-butylamino, 1-methylpropylamino, 2-methylpropylamino or 1,1-dimethylethylamino, in particular methylamino or ethylamino;

- di(C1-C4-alkyl)amino: N,N-dimethylamino, N,N-diethylamino, N,N-dipropylamino, N,N-di(1-methylethyl)amino, N,N-dibutyl-amino, N,N-di(l-methylpropyl)amino, N,N-di(2-methylpro-pyl)ami~no, N,N-di(1,1-dimethylethyl)amino, N-ethyl-N-methyl-amino,;N-methyl-N-propylamino, N-methyl-N-(1-methylethyl)-amino, N-butyl-N-methylamino, N-Methyl-N-(1-methylpropyl)-amino, N-methyl-N-(2-methylpropyl)amino, N-(1,1-dimethyl-ethyl)-N-methylamino, N-ethyl-N-propylamino, N-ethyl-N-(1-methylethyl)amino, N-butyl-N-ethylamino, N-ethyl-N-(1-methylpropyl)amino, N-ethyl-N-(2-methylpropyl)-amino, N-ethyl-N-(l,1-dimethylethyl)amino, N-(1-methyl-ethyl)-N-propylamino, N-butyl-N-propylamino, N-(1-methylpro-pyl)-N-propylamino, N-(2-methylpropyl)-N-propylamino, ~ N-(1,1-dimethylethyl)-N-propyl~m; no, N-butyl-N-(1-methyl-ethyl)amino, N-(1-methylethyl)-N-(1-methylpropyl)amino, N-(1-methylethyl)-N-(2-methylpropyl)amino, N-(1,1-dimethyl-ethyl)-N-(1-methylethyl)amino, N-butyl-N-(l-methylpropyl)-amino, N-butyl-N-(2-methylpropyl)amino, N-butyl-N-(1,1-dime-thylethyl)amino, N-(l-methylpropyl)-N-(2-methylpropyl)amino, N-(1,1-dimethyl- ethyl)-N-(1-methylpropyl)amino or N-(1,1-di-methyl- ethyl)-N-(2-methylpropyl)amino, in particular N(CH3) 2 or N(C2Hs)2;
~ - C1-C4-alkoxy-Cl-C~-alkyl: C1-C4-alkyl which is substituted by Cl-C4-alkoxy as mentioned above, i.e., for example, methoxy-methyl, ethoxymethyl, n-propoxymethyl, (1-methylethoxy)-methyl, n-butoxymethyl, (1-methylpropoxy)methyl, (2-methyl-propoxy)methyl, (1,1-dimethylethoxy)methyl, 2-(methoxy)ethyl, 2-(ethoxy)ethyl, 2-(n-propoxy)ethyl, 2-(1-methylethoxy)ethyl, 2-(n-butoxy)ethyl, 2-(1-methylpropoxy)ethyl, 2-(2-methylpro-poxy)ethyl, 2-(1,1-dimethylethoxy)ethyl, 2-(methoxy)propyl, 2-(ethoxy)propyl, 2-(n-propoxy)propyl, 2-(1-methylethoxy)pro-pyl, 2-(n-butoxy)propyl, 2-(1-methylpropoxy)propyl, 2-(2-methylpropoxy)propyl, 2-(1,1-dimethylethoxy)propyl, 3-(methoxy)propyl, 3-(ethoxy)propyl, 3-(n-propoxy)propyl, 3-(1-methylethoxy)propyl, 3-(n-butoxy)propyl, 3-~1-methylpro-poxy)propyl, 3-(2-methylpropoxy)propyl, 3-(1,1-dimethyl-ethoxy)propyl, 2-(methoxy)butyl, 2-(ethoxy)butyl, 2-(n-pro-poxy)butyl, 2-(1-methylethoxy)butyl, 2-(n-butoxy)butyl, 2-(1-methylpropoxy)butyl, 2-(2-methylpropoxy)butyl, 2-(1,1-dimethylethoxy)butyl, 3-(methoxy)butyl, 3-(ethoxy)butyl, 3-(n-propoxy)butyl, 3-(1-methylethoxy)butyl, 0050/46587 CA 0224~41 1998-08-06 3-(n-butoxy)butyl, 3-(1-methylpropoxy)butyl, 3-(2-methylpro-poxy)butyl, 3-(1,1-dimethylethoxy)butyl, 4-(methoxy)butyl, 4-(ethoxy)butyl, 4-(n-propoxy)butyl, 4-(1-methylethoxy)butyl, 4-(n-butoxy)butyl, 4-(1-methylpropoxy)butyl, 4-(2-methylpro-poxy)butyl or 4-(1,1-dimethylethoxy)butyl, in particular methoxymethyl or 2-methoxyethyl;
- (Cl-C4-alkoxy)carbonyl-Cl-C4-alkyl: Cl-C4-alkyl which is sub-stituted by (Cl-C4-alkoxy)carbonyl as mentioned above, i.e., for example, methoxycarbonylmethyl, ethoxycarbonylmethyl, l-(methoxycarbonyl)ethyl or 2-(methoxycarbonyl)ethyl;
- Cl-C4-alkylthio-Cl-C4-alkyl: Cl-C4-alkyl which is substituted by Cl-C4-alkylthio as mentioned above, i.e., for example, lS methylthiomethyl, ethylthiomethyl, n-propylthiomethyl, (l-methylethylthio)methyl, n-butylthiomethyl, (l-methylpro-pylthio)methyl, (2-methylpropylthio)methyl, (l,l-dimethyl-ethylthio)methyl, 2-methylthioethy~, 2-ethylthioethyl, 2-(n-propylthio)ethyl, 2-(1-methylethylthio)ethyl, 2-(n-bu-tylthio)ethyl, 2-(1-methylpropylthio)ethyl, 2-(2-methylpro-pylthio)ethyl, 2-(1,1-dimethylethylthio)ethyl, 2-(methyl-thio)propyl, 3-(methylthio)propyl, 2-(ethylthio)propyl, 3-(ethylthio)propyl, 3-(propylthio)propyl, 3-(butylthio)pro-pyl, 4-(methylthio)butyl, 4-(ethylthio)butyl, 4-(n-propyl-thio)butyl or 4-(n-butylthio)butyl, in particular 2-(methyl-thio)ethyl;
- (Cl-C4-alkylthio)carbonyl-Cl-C4-alkyl: Cl-C4-alkyl which is substituted ~y (Cl-C4-alkylthio)carbonyl such as (methyl-thio)carbonyl, (ethylthio)carbonyl, (n-propylthio)carbonyl, (l-methylethylthio)carbonyl, (n-butylthio)carbonyl, (l-methylpropylthio)carbonyl, (2-methylpropylthio)carbonyl and (l,l-dimethylethylthio)carbonyl, preferably (methyl-thio)carbonyl or (ethylthio)carbonyl, i.e., for example, (me-thylthio)carbonylmethyl, (ethylthio)carbonylmethyl, l-t(me-thylthio)carbonyl]ethyl or 2-[(methylthio)carbonyl]ethyl;
- Cl-C4-haloalkylthio-Cl-C4-alkyl: Cl-C4-alkyl as mentioned above which has attached to it a Cl-C4-alkylthio group which is partially or fully substituted by fluorine, chlorine and/
or bromine, e.g. difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, bromodifluoromethylthio, 2-fluoro-ethylthio, 2-chloroethylthio, 2-bromoethylthio, 2-iodoethyl-thio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2,2,2-trichloroethylthio, 2-chloro-2-fluoroethylthio, 2-chlo-ro-2,2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, pentafluoroethylthio, 2-fluoropropylthio, 3-fluoropropylthio, -0050/46587 CA 0224~41 l998-08-06 2-chloropropylthio, 3-chloropropylthio, 2-bromopropylthio, 3-bromopropylthio, 2,2-di~luoropropylthio, 2,3-di~luoropro-pylthio, 2,3-dichloropropylthio, 3,3,3-tri~luoropropylthio, 3,3,3-trichloropropylthio, 2,2,3,3,3-pentafluoropropylthio, heptafluoropropylthio, 1-(fluoromethyl)-2-~luoroethylthio, l-(chloromethyl)-2-chloroethylthio, 1-(bromomethyl)-2-bromo-ethylthio, 4-fluorobutylthio, 4-chlorobutylthio or 4-bromobu-tylthio, i.e., for example, di~luoromethylthiomethyl;
10 - Cl-C4-alkylamino-Cl-C4-alkyl: Cl-C4-alkyl which is substituted by Cl-C4-alkylamino as mentioned above, i.e., ~or example, methylaminomethyl, ethyl~m;nomethyl~ n-propyl~m;n~ethyl, (l-methylethylamino)methyl, n-butyl~minomethyl~ (l-methyl-propylamino)methyl, (2-methylpropylamino)methyl, (l,l-dime-thylethylamino)methyl, 2-methylaminoethyl, 2-ethylaminoethyl, 2-(n-propylamino)ethyl, 2-(1-methylethylamino)ethyl, 2-(n-butylamino)ethyl, 2-~1-methylpropylamino)ethyl, 2-(2-methylpropylamino)ethyl, 2-(1,1-dimethylethyl ~m; no) -ethyl, 2-(methylamino)propyl, 3-(methylamino)propyl, 2-(ethylamino)propyl, 3-(ethylamino)propyl, 3-(propyl ~m; no)propyl, 3-(butylamino)propyl, 4-(methylamino)butyl, 4-(ethylamino)butyl, 4-(n-propylamino)butyl ~or 4-(n-butylamino)butyl, ~in ~particular 2-(methylamino)ethyl;
a5 - Cl-C~-alkylaminocarbonyl-Cl-C4-a~kyl: Cl-C4-alkyl which is substituted by Cl-C4-alkylaminocarbonyl such as methylamino-carbonyl, ethylaminocarbonyl, n-propylaminocarbonyl, l-methy-lethylaminocarbonyl, n-butylaminocarbonyl, l-methylpropylami-nocarbonyl, 2-methylpropylaminocarbonyl or l,l-dimethylethyl-aminocarbonyl, preferably methylaminocarbonyl or ethylamino-carbonyl, i.e., for example, (methylaminocarbonyl)methyl, (ethylaminocarbonyl)methyl, l-(methylaminocarbonyl)ethyl or 2-(methylaminocarbonyl)ethyl;
3~
- di(Cl-C4-alkyl)amino-Cl-C4-alkyl: Cl-C4-alkyl which is substi-tuted by di(Cl-C4-alkyl)amino as mentioned above, i.e., ~or example, dimethylaminomethyl or diethylaminomethyl;
40 - di(Cl-C4-alkyl)aminocarbonyl-Cl-C4-alkyl: Cl-C4-alkyl which i~
substituted by di(Cl-C4-alkyl)aminocarbonyl such as N,N-dime-thyl~;nocarbonyl, N,N-diethylaminocarbonyl, N,N-dipropylami-nocarbonyl, N,N-di(l-methylethyl)aminocarbonyl, N,N-dibutyl-aminocarbonyl, N,N-di(l-methylpropyl)aminocarbonyl, N,N-di(2-methylpropyl)aminocarbonyl, N,N-di(l,l-dimethyl-ethyl)aminocarbonyl, N-ethyl-N-methylaminocarbonyl, N-methyl-N-propylaminocarbonyl, N-methyl-N-(l-methylethyl)aminocarbo-0050/46587 CA 0224~41 l998-08-06 nyl, N-butyl-N-methylaminocarbonyl, N-methyl-N-(1-methylpro-pyl)aminocarbonyl, N-methyl-N-(2-methylpropyl)aminocarbonyl, N-~1,1-dimethylethyl)-N-methylaminocarbonyl, N-ethyl-N-propy-laminocarbonyl, N-ethyl-N-(l-methylethyl)aminocarbonyl, N-butyl-N-ethylaminocarbonyl, N-ethyl-N-(1-methylpropyl)-- aminocarbonyl, N-ethyl-N-(2-methylpropyl)aminocarbonyl, N-ethyl-N-(l,l-dimethylethyl)aminocarbo~yl, N-(l-methyl-ethyl)-N-propyl~ ocarbonyl, N-butyl-N-propylaminocarbonyl, N-(l-methylpropyl)-N-propylaminocarbonyl, N-(2-methyl-propyl)-N-propyl- aminocarbonyl, N-(1,1-dimethylethyl)-N-propylaminocarbonyl, N-butyl-N-(1-methylethyl)aminocarbonyl, N-(1-methylethyl)- N-(l-methylpropyl)aminocarbonyl, N-(1-methylethyl)-N-(2-methylpropyl)aminocarbonyl, N-(1,1-di-methylethyl)-N-(1-methylethyl)aminocarbonyl, N-butyl-N-(1-methylpropyl)aminocarbonyl, N-butyl-N-(2-methyl-propyl)aminocarbonyl, N-butyl-N-(1,1-dimethylethyl)amino-carbonyl, N-(1-methylpropyl)-N-(2-methylpropyl)aminocarbonyl, N-(1,1-dimethylethyl)-N-(1-methylpropyl)aminocarbonyl or N-(1,1-dimethylethyl)-N-(2-methylpropyl)aminocarbonyl, preferably N,N-dimethylaminocarbonyl or N!N-diethylamino-carbonyl, i.e., for example, dimethylaminocarbonylmethyl, diethylaminocarbonylmethyl, 1-(dimethylaminocarbonyl)ethyl or 2-(dimethylaminocarbonyl)ethyl;
25 - Cl-C4-alkylsulfinyl-C1-C4-alkyl: Cl-C4-alkyl which is substi-tuted by methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, 1-methylethylQul~inyl, n-butylsulfinyl, 1-methylpropylsulfi-nyl, 2-methylpropylsulfinyl or 1,1-dimethylethylsulfinyl, preferably methylsulfinyl, i.e, for example, methylsulfinyl-methyl or 2-methylsulfinylethyl;
- Cl-C4-haloalkylsulfinyl-C1-C4-alkyl: Cl-~4-alkyl as mentioned above which has attached to it a Cl-C4-alkylsulfinyl group which is partially or fully substituted by fluorine, chlorine and/or bromine, e.g. difluoromethylsulfinyl, trifluoromethyl-sulfinyl, chlorodifluoromethylsulfinyl, bromodifluoromethyl-sulfinyl, 2-fluoroethylsulfinyl, 2-chloroethylsulfinyl, 2-bromoethylsulfinyl, 2-iodoethylsulfinyl, 2,2-difluoroethyl-sulfinyl, 2,2,2-trifluoroethylsulfinyl, 2,2,2-trichloroethyl-sulfinyl, 2-chloro-2-fluoroethylsulfinyl, 2-chloro-2,2-di-fluoroethylsulfinyl, 2,2-dichloro-2-fluoroethylsulfinyl, pen-tafluoroethylsulfinyl, 2-fluoropropylsulfinyl, 3-fluoropro-pylsulfinyl, 2-chloropropylsulfinyl, 3-chloropropylsulfinyl, 2-bromopropylsulfinyl, 3-bromopropylsulfinyl, 2,2-difluoro-propylsulfinyl, 2,3-difluoropropylsul~inyl, 2,3-dichloropro-pylsulfinyl, 3,3,3-trifluoropropylsulfinyl, 3,3,3-trichloro-propylsulfinyl, 2,2,3,3,3-pentafluoropropylsulfinyl, hepta-_ _ _ _ ~ 0050/46587 CA 0224~4l l998-08-06 .~

fluoropropylsulfinyl, l-(fluoromethyl)-2-fluoroethylsulfinyl, l-(chloromethyl)-2-chloroethylsulfinyl, 1-(bromomethyl)-2-bromoethylsulfinyl, 4-fluorobutylsulfinyl, 4-chlorobutyl-sulfinyl or 4-bromobutylsulfinyl, i.e., for example, difluo-romethylsulfinylmethyl;
- C1-C4-alkylsulfonyl: methylsulfonyl, ethylsulfonyl, n-propyl-sulfonyl, 1-methylethylsulfonyl, n-butylsulfonyl, l-methyl-propylsulfonyl, 2-methylpropylsulfonyl or 1,1-dimethylethyl-sulfonyl, in particular methylsulfonyl or ethylsulfonyl;
- Cl-C4-alkylsulfonyl-C1-C4-alkyl: C1-C4-alkyl which is substi-tuted by C1-C4-alkylsulfonyl as mentioned above, preferably methylsulfonyl, i.e., for example, methylsulfonylmethyl or 2-methylsulfonylethyl;
- C1-C4-haloalkylsulfonyl-Cl-C4-alkyl: Cl-C4-alkyl as mentioned above which has attached to it a C1-C4-alkylsulfonyl group which is partially or fully substituted by fluorine, chlorine and/or bromine, e.g. difluoromethylsulfonyl, trifluoromethyl-sulfonyl, chlorodifluoromethylsulfonyl, bromodifluoromethyl-sul~onyl, 2-fluoroethylsulfonyl, 2-chloroethylsulfonyl, 2-bromoethylsulfonyl, 2-iodoethylsulfonyl, 2,2-difluoroethyl-sulfonyl, 2,2,2-trifluoroethylsulfonyl, 2,2,2-trichloroethyl-sulfonyl, 2-chloro-2-fluoroethylsulfonyl, 2-chloro-2,2-~i-fluoroethylsulfonyl, 2,2-dichloro-2-fluoroethylsulfonyl, pen-tafluoroethylsulfonyl, 2-fluoropropylsulfonyl, 3-fluoropro-pylsulfonyl, 2-chloropropylsulfonyl, 3-chloropropylsulfonyl, 2-bromopropylsulfonyl, 3-bromopropylsulfonyl, 2,2-difluoro-propylsulfonyl, 2,3-difluoropropylsulfonyl, 2,3-dichloropro-pylsulfonyl, 3,3,3-trifluoropropylsulfonyl, 3,3,3-trichloro-propylsulfonyl, 2,2,3,3,3-pentafluoropropylsulfonyl, hepta-fluoropropylsulfonyl, 1-(fluoromethyl)-2-fluoroethylsulfonyl, 1-(chloromethyl)-2-chloroethylsulfonyl, l-(bromomethyl)-2-bromoethylsulfonyl, 4-fluorobutylsulfonyl, 4-chlorobutyl-sulfonyl or 4-bromobutylsulfonyl, i.e., for example, 2-chlo-roethylsul~onyl;
- C3-C6-alkenyl: for example prop-2-en-1-yl, n-buten-4-yl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl, 2-buten-1-yl, n-penten-3-yl, n-penten-4-yl, 1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl, 3-methylbut-2-en-1-yl, 1-methyl-but-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl, 1,1-dimethylprop-2-en-1-yl, 1,2-dimethylprop-2-en-1-yl, 1-ethylprop-2-en-1-yl, n-hex-3-en-1-yl, n-hex-4-en-1-yl, n-hex-5-en-1-yl, 1-methylpent-3-en-1-yl, 2-methyl-pent-3-en-1-yl, 3-methylpent-3-en-1-yl, 4-methyl-' 0050/46~87 CA 0224~41 l998-08-06 i pent-3-en-1-yl, 1-methylpent-4-en-1-yl, 2-methyl-pent-4-en-1-yl, 3-methylpent-4-en-1-yl, 4-methyl-pent-4-en-1-yl, 1,1-dimethylbut-2-en-1-yl, 1,1-dimethyl-but-3-en-1-yl, 1,2-dimethylbut-2-en-1-yl, 1,2-dimethyl-but-3-en-1-yl, 1,3-dimethylbut-2-en-1-yl, 1,3-dimethyl-but-3-en-1-yl, 2,2-dimethylbut-3-en-1-yl, 2,3-dimethyl-but-2-en-1-yl, 2,3-dimethylbut-3-en-1-yl, 3,3-dimethyl-but-2-en-1-yl, 1-ethylbut-2-en-l-yl, 1-ethylbut-3-en-1-yl, 2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl, 1,1,2-trimethyl-prop-2-en-1-yl, 1-ethyl-1-methylprop-2-en-1-yl or 1-ethyl-2-methylprop-2-en-1-yl, in particular prop-2-en-1-yl or n-buten-4-yl;
- C3-C6-haloalkenyl: C3-C6-alkenyl as mentioned above which is 1~ partially or fully substituted by fluorine, chlorine and/or bromine, i.e., for example, 2-chloroallyl, 3-chloroallyl, 2,3-dichloroallyl, 3,3-dichloroallyl, 2,3,3-trichloroallyl, 2,3-dichlorobut-2-enyl, 2-bromoallyl, 3-bromoallyl, 2,3-di-brom~allyl, 3,3-dibromoallyl, 2,3,3-tribromoallyl or 2,3-di-bromobut-2-enyl, in particular 2-chloroallyl or 3,3-dichlo-roallyl;
- cyano-C3-C6-alkenyl: ~or example 3-cyanoallyl, 4-cyano-but-2-enyl, 4-cyanobut-3-enyl or 5-cyanopent-4-enyl, prefer-ably 3-cyanoallyl or 4-cyanobut-2-enyl, in particular 3-cya-noallyl;
.

- C3-C4-alkenyloxy-C1-C4-alkyl: C1-C4-alkyl which i~ substituted by C3-C4-alkenyloxy such as prop-2-enyloxy, n-but-2-enyloxy, n-but-3-enyloxy, 1-methylprop-2-enyloxy or 2-methylprop-2-enyloxy, preferably allyloxy, 2-methylprop-2-en-1-yloxy, but-1-en-3-yloxy, but-1-en-4-yloxy or but-2-en-1-yloxy, i.e., for example, allyloxymethyl, 2-allyloxyethyl or but-1-en-4-yloxymethyl;
- C3-C4-alkenylthio-C1-C4-alkyl: C1-C4-alkyl which is substi-tuted by C3-C4-alkenylthio such as prop-2-enylthio, n-but-2-enylthio, n-but-3-enylthio, 1-methylprop-2-enylthio or 2-methylprop-2-enylthio, preferably allylthio, 2-methyl-prop-2-en-1-ylthio, but-1-en-3-ylthio, but-1-en-4-ylthio or but-2-en-1-ylthio, i.e., for example, allylthiomethyl, 2-allylthioethyl or but-1-en-4-ylthiomethyl;
- C3-C4-alkenylsulfinyl-C1-C4-alkyl: C1-C4-alkyl which is sub-stituted by C3-C4-alkenylsulfinyl such as prop-2-enylsulfinyl, n-but-2-enylsulfinyl, n-but-3-enylsulfinyl, 1-methyl-prop-2-enylsulfinyl or 2-methylprop-2-enylsulfinyl, prefer-- -Q050/46587 CA 0224~41 1998-08-06 ably allylsulfinyl, 2-methylprop-2-en-1-ylsulfinyl, but-l-en-3-ylsulfinyl, but-1-en-4-ylsulfinyl or but-2-en-1-ylsulfinyl, i.e., for example, allylsulfinyl-methyl, 2-allylsul~inylethyl or but-1-en-4-ylsulfinylmethyl;
- C3-C4-alkenylsulfonyl-Cl-C4-alkyl: C1-C4-alkyl which is sub-stituted by C3-Cg-alkenylsUl~onyl such as prop-2-enylsulfonyl, n-but-2-enylsulfonyl, n-but-3-enylsulfonyl, 1-methylprop-2-enylsulfonyl or 2-methylprop-2-enylsul~onyl, pre~erably allylsulfonyl, 2-methylprop-2-en-1-ylsulfonyl, but-1-en-3-yl-sulfonyl, but-1-en-4-ylsulfonyl or but-2-en-1-ylsulfonyl, i.e., for example, allylsulfonylmethyl, 2-allylsulfonylethyl or but-1-en-4-ylsulfonylmethyl;
15 - C3-C6-alkynyl: for example propargyl, n-but-1-yn-3-yl, n-but-1-yn-4-yl, n-but-2-yn-1-yl, n-pent-1-yn-3-yl, n-pent-l-yn-4-yl, n-pent-1-yn-5-yl, n-pent-2-yn-1-yl, n-pent-2-yn-4-yl, n-pent-2-yn-5-yl, 3-methyl-but-1-yn-3-yl, 3-methyl-but-1-yn-4-yl, n-hex-1-yn-3-yl, n-hex-1-yn-4-yl, ao n-hex-1-yn-5-yl, n-hex-1-yn-6-yl, n-hex-2-yn-1-yl, n-hex-2-yn-4-yl, n-hex-2-yn-5-yl, n-hex-2-yn-6-yl, n-hex-3-yn-1-yl, n-hex-3-yn-2-yl, 3-methylpent-1-yn-3-yl, 3-methylpent-1-yn-4-yl, 3-methylpent-1-yn-5-yl, 4-methyl-pent-2-yn-4-yl or 4-methylpent-2-yn-5-yl, in particular pro-pargyl;
- C3-C6-haloalkynyl: C3-C6-alkynyl as mentioned above which is partially or fully substituted by fluorine, chlorine and/or bromine, i.e., ~or example, 1,1-difluoroprop-2-yn-1-yl, 4-fluorobut-2-yn-1-yl, 4-chlorobut-2-yn-1-yl, 1,1-difluoro-but-2-yn-1-yl, 5-~luoropent-3-yn-1-yl or 6-fluorohex-4-yn-1--yl;
- cyano-C3-C6-alkynyl: for example 3-cyanopropargyl;
- C3-C4-alkynyloxy-Cl-C4-alkyl: C1-C4-alkyl which is substitute~
by C3-C4-alkynyloxy such as prop-2-ynyloxy, n-but-2-ynyloxy, n-but-3-ynyloxy or 1-methylprop-2-ynyloxy, preferably propar-gyloxy, but-1-yn-3-yloxy, but-1-yn-4-yloxy or but-2-yn-1-yloxy, i.e., for example, propargyloxymethyl or 2-propar-gyloxyethyl;
- C3-C4-alkynylthio-Cl-C~-alkyl: C1-C~-alkyl which is substi-tuted by C3-C4-alkynylthio such as prop-2-ynylthio, n-but-2-ynylthio, n-but-3-ynylthio or 1-methylprop-2-ynyl-thio, preferably propargylthio, but-1-yn-3-ylthio, but-1-yn-4-ylthio or but-2-yn-1-ylthio, i.e., for example, 0050/46587 CA 0224~41 l998-08-06 propargylthiomethyl or 2-propargylthioethyl;
- C3-C4-alkynylsul~inyl-Cl-C4-alkyl: C1-C4-alkyl which is sub-stituted by C3-C4-alkynylsul~inyl such as prop-2-ynylsul~inyl, n-but-2-ynylsul~inyl, n-but-3-ynylsulfinyl and 1-methyl-prop-2-ynylsul~inyl, preferably propargylsulfinyl, but-1-yn-3-ylsulfinyl, but-1-yn-4-ylsulfinyl or but-2-yn-1-ylsul~inyl, i.e., for example, propargylsul~inyl-methyl or 2-propargylsulfinylethyl;
- C3-C4-alkynylsulfonyl-Cl-C4-alkyl: C1-C4-alkyl which is sub-stituted by C3-C4-alkynylsulfonyl such as prop-2-ynyl~ul~onyl, n-but-2-ynylsulfonyl, n-but-3-ynylsul~onyl and 1-methyl-prop-2-ynylsulfonyl, preferably propargylsulfonyl, but-1-yn-3-ylsul~onyl, but-1-yn-4-ylsulfonyl or but-2-yn-1-yl~ul~onyl, i.e., for example, propargylsulfonyl-methyl or 2-propargylsul~onylethyl;
- C3-Cg-cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl, cyclo-hexyl, cycloheptyl or cyclooctyl, in particular cyclopentylor cyclohexyl;
- C3-C8-cycloalkyl-C1-C4-alkyl: cyclopropylmethyl, cyclobutyl-methyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptyl-methyl, cyclooctylmethyl, 1-(cyclopropyl)ethyl, 1-(cyclo-butyl)ethyl, l-(cyclopentyl)ethyl, 1-(cyclohexyl)ethyl, 1-(cycloheptyl)ethyl, l-(cyclooctyl)ethyl, 2-(cyclopro-pyl)ethyl, 2-(cyclobutyl)ethyl, 2-(cyclopentyl)ethyl, 2-(cyclohexyl)ethyl, 2-(cycloheptyl)ethyl, 2-(cyclooctyl)ethyl, 3-(cyclopropyl)propyl, 3-(cyclo-butyl)propyl, 3-(cyclopentyl)propyl, 3-(cyclohexyl)propyl, 3-(cycloheptyl)propyl, 3-(cyclooctyl)propyl, 4-(cyclo-propyl)butyl, 4-(cyclobutyl)butyl, 4-(cyclopentyl)butyl, 4-(cyclohexyl)- butyl, 4-(cycloheptyl)butyl or 4-(cyclooctyl)butyl, in particular cyclopentylmethyl or cyclohexylmethyl;
- C3-C8-cycloalkoxy-C1-C4-alkyl: cyclopropyloxymethyl, cyclobu-tyloxymethyl, cyclopentyloxymethyl, cyclohexyloxymethyl, cycloheptyloxymethyl, cyclooctyloxymethyl, 1-(cyclopropyl-oxy)ethyl, l-(cyclobutyloxy)ethyl, 1-(cyclopentyloxy)ethyl, 1-(cyclohexyloxy)ethyl, 1-(cycloheptyloxy)ethyl, 1-(cyclooc-tyloxy)ethyl, 2-(cyclopropyloxy)ethyl, 2-(cyclobuty-loxy)ethyl, 2-(cyclopentyloxy)ethyl, 2-(cyclohexyloxy)ethyl, 2-(cycloheptyloxy)ethyl, 2-(cyclooctyloxy)ethyl, 3-(cyclopro-pyloxy)propyl, 3-(cyclobutyloxy)propyl, 3-(cyclopenty-loxy)propyl, 3-(cyclohexyloxy)propyl, 3-(cycloheptyloxy)pro-_ 0050/46587 CA 02245~4l 1998-08-06 pyl, 3-(cyclooctyloxy)propyl, 4-(cyclopropyloxy)butyl, 4-(cyclobutyloxy)butyl, 4-(cyclopentyloxy)butyl, 4-(cyclohex-yloxy)butyl, 4-(cycloheptyloxy)butyl or 4-(cyclooctyloxy)bu-tyl, in particular cyclopentyloxymethyl, cyclohexyloxymethyl or 2-(cyclopentyloxy)ethyl.
3- to 7-membered heterocyclyl is to be understood a~ m~n; ng both saturated, partially or fully unsaturated and aromatic hetero-cycles having one to three hetero atoms selected from a group 10 consisting of - one to three nitrogen atoms, - one or two oxygen and - one or two sulfur atoms.
15 Examples of saturated heterocycles which can contain a c~rh~nyl or thiocarbonyl ring member are:
oxiranyl, thiiranyl, aziridin-1-yl, aziridin-2-yl, diaziri-din-1-yl, diaziridin-3-yl, oxetan-2-yl, oxetan-3-yl, thietan-2-yl, thietan-3-yl, azetidin-1-yl, azetidin-2-yl, ao azetidin-3-yl, tetrahydro~uran-2-yl, tetrahydrofuran-3-yl, tetra-hydrothiophen-2-yl, tetrahydrothiophen-3-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-3-yl, 1,3-dioxolan-2-yl, 1,3-dioxo-lan-4-yl, 1,3-oxathiolan-2-yl, 1,3-oxathiolan-4-yl, 1,3-oxathio-lan-5-yl, 1,3-oxazolidin-2-yl, 1,3-oxazolidin-3-yl, 1,3-oxazoli-25 din-4-yl, 1,3-oxazolidin-5-yl, 1,2-oxazolidin-2-yl, 1,2-oxazoli-din-3-yl, 1,2-oxazolidin-4-yl, 1,2-oxazolidin-5-yl, 1,3-dithio-lan-2-yl, 1,3-dithiolan-4-yl, pyrrolidin-1-yl, pyrrolidin-2-yl, pyrrolidin-5-yl, tetrahydropyrazol-1-yl, tetrahydropyrazol-3-yl, tetrahydropyrazol-4-yl, tetrahydropyran-2-yl, tetrahydropy-30 ran-3-yl, tetrahydropyran-4-yl, tetrahydrothiopyran-2-yl, tetra-hydrothiopyran-3-yl, tetrahydropyran-4-yl, piperidin-1-yl, piper-idin-2-yl, piperidin-3-yl, piperidin-4-yl, 1,3-dioxan-2-yl, 1,3-dioxan-4-yl, 1,3-dioxan-5-yl, 1,4-dioxan-2-yl, 1,3-oxathian-2-yl, 1,3-oxathian-4-yl, 1,3-oxathian-5-yl, 35 1,3-oxathian-6-yl, 1,4-oxathian-2-yl, 1,4-oxathian-3-yl, morpho-lin-2-yl, morpholin-3-yl, morpholin-4-yl, hexahydropyrida-zin-1-yl, hexahydropyridazin-3-yl, hexahydropyridazin-4-yl, hexa-hydropyrimidin-1-yl, hexahydropyrimidin-2-yl, hexahydropyrimi-din-4-yl, hexahydropyrimidin-5-yl, piperazin-1-yl, pipera-40 zin-2-yl, piperazin-3-yl, hexahydro-1,3,5-triazin-1-yl, hexahy-dro-1,3,5-triazin-2-yl, oxepan-2-yl, oxepan-3-yl, oxepan-4-yl, thiepan-2-yl, thiepan-3-yl, thiepan-4-yl, 1,3-dioxepan-2-yl, 1,3-dioxepan-4-yl, 1,3-dioxepan-5-yl, 1,3-dioxepan-6-yl, 1,3-di-thiepan-2-yl, 1,3-dithiepan-2-yl, 1,3-dithiepan-2-yl, 1,3-dithie-45 pan-2-yl, 1,4-dioxepan-2-yl, 1,4-dioxepan-7-yl, hexahydroaze-pin-1-yl, hexahydroazepin-2-yl, hexahydroazepin-3-yl, hexahydroa-zepin-4-yl, hexahydro-1,3-diazepin-1-yl, hexahydro-1,3-diaze-_ 0050/46587 CA 0224~541 l998-08-06 pin-2-yl, hexahydro-1,3-diazepin-4-yl, hexahydro-1,4-diaze-pin-1-yl and hexahydro-1,4-diazepin-2-yl;
Examples of unsaturated heterocycles which can contain a carbonyl 5 or thiocarbonyl ring me-m-~er are:
dihydrofuran-2-yl, 1,2-oxazolin-3-yl, 1,2-oxazolin-5-yl, 1,3-oxa-zolin-2-yl;
Preferred amongst the heteroaromatics are those having S or 6 10 members, i.e., for example, furyl such as 2-furyl and 3-furyl, thienyl such as 2-thienyl ~nd 3-thienyl, pyrrolyl such as 2-pyr-rolyl and 3-pyrrolyl, isoxazolyl such as 3-isoxazolyl, 4-isoxazo-lyl and 5-isoxazolyl, isothiazolyl such as 3-isothiazolyl, 4-iso-thiazolyl and 5-isothiazolyl, pyrazolyl such as 3-pyrazolyl, 15 4-pyrazolyl and 5-pyrazolyl, oxazolyl such as 2-oxazolyl, 4-oxa-zolyl and 5-oxazolyl, thiazolyl such as 2-thiazolyl, 4-thiazolyl and 5-thiazolyl, imidazolyl such as 2-imidazolyl and 4-imidazo-lyl, oxadiazolyl such as 1,2,4-oxadiazol-3-yl, 1,2,4-oxadia-zol-5-yl and 1,3,4-oxadiazol-2-yl, thiadiazolyl such as 20 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl and 1,3,4-thiadia-zol-2-yl, triazolyl such as 1,2,4-triazol-1-yl, 1,2,4-tria-zol-3-yl and 1,2,4-triazol-4-yl, pyridinyl such as 2-pyridinyl, 3-pyridinyl and 4-pyridinyl, pyridazinyl such as 3-pyridazinyl and 4-pyridazinyl, pyrimidinyl such as 2-pyrimidinyl, 4-pyrimidi-25 nyl and 5-pyrimidinyl, furthermore 2-pyrazinyl, 1,3,5-triazin-2-yl and l,2,4-triazin-3-yl, in particular pyridyl, pyrimidyl, furanyl and thienyl.
All phenyl and heterocyclic rings are preferably unsubstituted or 30 have attached to them a cyano, nitro, halogen, C1-C4-alkyl, C1-Cg-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, (C1-C4-alkyl)car-bonyl, (Cl-C~-alkoxy)carbonyl or (C1-C4-alkyl)carbonyloxy substi-tuent.
35 With a view to the use of the substituted 2-phenylpyridines I as herbicides or for the desiccation/defoliation of plants, pre-ferred compounds I are those where the substituents have the fol-lowing me~n;ngs~ in each case alone or in com.bination:
40 X is 1,2-ethyndiyl, methylene, 1,2-et~Ane~;yl, methyleneoxyme-thylene, ethene-1,2-diyl, or oxymethylene which is bonded to the phenyl ring via the hetero atom, it being possible for the last-mentioned 5 bridges to have attached, to the carbon atom adjacent to the phosphorus, one of the following substi-tuents: cyano, halogen, C1-C4-alkyl or (C1-C4-alkoxy)carbonyl;

-in particular -CH2-, -CHaCH2-, -CH2-CH(halogen)-, -CH2-CH(CN)-, -CH2-CH(CH3)-, -CH2-CH(COOCH3)-, -CH2-O-CH2-, -CH=CH-, -CH=C(halogen)-, -CH=C(CN)-, -CH=C(CH3)-, -CH=C(COOCH3)-, -CH2-CH(COOCH3)- or -OCH2-;
especially preferably -CH2-CH(halogen)- or -CH=C(halogen)-;
Y is oxygen; Zl i5 oxygen; z2 is oxygen;
R1, R2, R7 and R8, independently of one another, are 10 hydrogen, C1-C6-alkyi, C1-C6-haloalkyl, cyano-Cl-C4-alkyl, Cl-C4-alkoxy-Cl-C4-alkyl, di(C1-C4-alkyl)amino-C1-C4-alkyl, Cl-C4-alkylthio-Cl-C4-alkyl, Cl-C4-alkylsulfonyl-Cl-C4-alkyl, Cl-C4-haloalkylsul~onyl-Cl-C4-alkyl, C3-C6-alkenyl, C3-C6-haloalke-nyl, C3-C6-alkynyl, hydroxycarbonyl-C1-C4-alkyl, (Cl-C4-alkoxy)car-15 bonyl-Cl-C4-alkyl, aminocarbonyl-Cl-C4-alkyl, (Cl-C4-alkyl)amino-carbonyl-C1-C4-alkyl, di(C1-C4-alkyl)aminocarbonyl-C1-C4-alkyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, phenyl, phenyl-Cl-C4-alkyl or 3- to 7-membered heterocyclyl or heterocyclyl-Cl-C4-alkyl, it being possible for all heterocycles, i~ desired, 20 to contain a carbonyl or thiocarbonyl ring member and it being possi~le ~or all cycloalkyl, phenyl and heterocyclyl rings to be unsubstituted or to have attached to them one to four substitu-ents, in each case selected from the group consisting of halogen, nitro, amino, hydroxyl, carboxyl, C1-C4-alkyl, C1-C4-haloalkyl, as Cl-C4-alkoxy, Cl-C4-alkylsul~onyl, (Cl-C4-alkyl)carbonyl, (C1-C4-alkoxy)carbonyl and di(C1-C4-alkyl)amino, or R1 and R2 or R1 and R7 and/or R2 and R8 in each case together form a 30 1,2-e~h~ne~;yl, 1,3-propylene, tetramethylene, pentamethylene or ethyleneoxyethylene chain which, if desired, can be substituted by one to four Cl-C4-alkyl groups and/or one or two (C1-C4-alkoxy)carbonyl groups;
35 in particular hydrogen, C1-C6~alkyl, C1-C6-haloalkyl, C3-C6-alke-nyl, C3-C6-haloalkenyl, C3-C6-alkynyl, (Cl- C4- alkoxy)carbonyl-C1-C4-alkyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-Cl-C4-alkyl, phe-nyl, phenyl-C1-C4-alkyl, 3- to 7-membered heterocyclyl or hetero-cyclyl-Cl-C4-alkyl, 40 or R1 and R2 and/or R1 and R7 and/or R2 and R8 in each case together form a 1,2-ethanediyl- or 1,3-propylene chain;
especially preferably hydrogen, Cl-C6-alkyl, C3-C6-alkenyl, C3 -C6-alkynyl, C3-C8-cycloalkyl, phenyl or phenyl-C1-C4-alkyl, or Rl and R2 together form a 1,3-propylene chain;
R3 is cyano, halogen or trifluoromethyl, in particular cyano or chlorine, especially preferably chlorine;

, 0050/46587 CA 0224554l l998-08-06 R4 iS hydrogen, ~luorine or chlorine, in particular hydrogen or ~ luorine;
5 R5 is chlorine;
R6 i8 chlorine or trifluoromethyl, in particular tri~luoro-methyl;
10 n iB zero.
Very especially pre~erred are the compounds Iaa ( ~ I where X = methylene; R3, R5 = chlorine; R4 = hydrogen; R6 = trif luorome-thyl; n = 0) which are listed in Table 1 below:
Table 1 ~ z2R2 Ia a No. --P(=Y)(Z lRI)(Z2R2 25 Iaa. 1 --P(=O)(OH)2 Iaa. 2 --p(=O)(OCH3)2 Iaa. 3 --P(=~)(~C2Hs)2 Iaa. 4 --P(=O)[O~C3H7)]2 3 o Iaa, S --P(=O)tOCH(CH3)2l2 Iaa. 6 --p(=o)[O~C4Hg)]2 Iaa. 7 --P(=o)[ocH2-cH(cH3)2]2 Iaa. 8 --P(=~)[~CH(CH3}C2Hs]2 35 Iaa. 9 _p(=o)(ocH2{~F3)2 Iaa. 10 _P(=o)(ocH2-cH2-oH)2 Iaa. 11 --P(=O)(OCH2-CH2 CN)2 Iaa. 12 _P(=o)(ocH2-cH2-ocH3)2 Iaa. 13 --P(=O)(OCH~CH2-Oc2Hs)2 Iaa. 14 _P(=o)(ocH2-cH2-ocF3)2 Iaa. 15 _P(=o)(ocH2-cH2-ocH2--CH=CH2)2 Iaa. 16 --P(=O)(OCH2-CH2~CH2--C----CH)2 Iaa. 17 --P(=o)(ocH2-cH2~cyclopentyl)2 Iaa. 18 _P(=O)(OCH2-CH2--NH2)2 Iaa. 19 --P(=o)(ocH2-cH2-NH--CH3)2 No. --P(=Y)(ZIRI)(Z2R2) Iaa. 20 ~P(=O)[OCH2-CH2-N(CH3)2]2 Iaa. 21 ~(=O)(OCH2-CH2 SCH3)2 Iaa. 22 ~P(=O)(OCH2-CH2~C2Hs)2 Iaa. 23 :P(=O)(OCH2-CH2~CF3)2 Iaa. 24 ~(=O)(OCHz-CH2~CH2-CH=CH2)2 Iaa. 25 ~(=O)(ocH2-cH2~cH2-c----CH)2 Iaa. 26 ~(=O)(OCH2-CH2~CH~C5CH)2 Iaa. 27 ~(=O)(OCH2-CH2~O-C2Hs)2 Iaa. 28 ~:P(=o)(ocH2~o2-cH3)2 Iaa. 29 ~(=O)(OCH2~02-C2HS)2 Iaa, 30 ~P(=O)(OCH2-CH2~O2-CH3)2 Iaa. 31 ~?(=O)(OCH2-CH~S02-c2H5)2 Iaa. 32 ~(=O)(OCH2--CH=CH2)2 Iaa. 33 ~(=O)(OCH2-CH=CH-CH3)2 2 o Iaa. 34 ~(=O)(OCHz-CH2-CH=CH2)2 Iaa. 35 --P(=o)(ocH2-cH=cH-cl)2 Ia~ 36 ~(=O)(OCH~C--CH)2 Iaa. 37 --P(=O)[OCH(CH3) C 5 CHk Iaa. 38 ~?(-o)(ocH2-co-ocH3)2 Iaa. 39 3?(=O)(OCH2-CO~C2Hs)2 Iaa. 40 ~(=O)[OCH(CH3~CO-OCH3]2 Iaa. 41 ~(=O)[OCH(CH3~CO-OC2H5]2 Iaa. 42 ~?(=O)(OCH2-CO NH2)2 Iaa. 43 ~P(=O)(OCH2-CO~H-CH3)2 Iaa. 44 --p(=O)[OCH2-CO N(CH3)2]2 Iaa. 45 ~P(=O)[OCH(CH3~CO~H2]2 3 Iaa. 46 --P(=O)[OCH(CH3~CO NH-CH3]2 Iaa. 47 ~?(=O)[OCH(CH3~CO~(CH3)2]2 Iaa. 48 ~(=O)(O-cyclopropyl)2 Iaa. 49 ~(=O)(O-cyclobutyl)2 Iaa. 50 --P(=O)(O-cyclopentyl)2 Iaa. 51 ~(=o)(o-cyclohexyl)2 Iaa. 52 ~e(=o)(ocH2~yclopropyl)2 Iaa. 53 --P(=O)(OCH2-cyclobutyl)2 Iaa. 54 ~(=O)(OCH2-cyclopentyl)2 Iaa. 55 ~(=o)(ocH2-cyclohexyl)2 Iaa. 56 ~P(=O)(O-phenyl)2 No. --P(=Y)(Z1R1)(Z2R2) Iaa. 57 ~p(=o)(ocH2i~henyl)2 Iaa. 58 ~(=O)(~oxet~u}3 yl) 2 5 Iaa. S9 ~(=O)(O~etraLy~vru'ai~2--yl) 2 Iaa. 60 ~?(=O)(O~e~aL~u~ ~Yl) 2 Iaa. 61 --P(=O)(O~etrallr~llv~rl~2--yl) 2 Iaa. 62 ~P(=O)(O~etrahyvhupyla~yl) 2 10 Iaa. 63 ~(=O)(O~etrallyll~vpyl~yl) 2 Iaa. 64 --P(=O)(OCHz-oxi~2--yl) 2 Iaa. 65 ~(=O)(OCH2~xeta~yl) 2 Iaa. 66 ~(=O)(OCH2~etrahydrûfuIa~2--Yl) 2 Iaa. 67 ~?(=O)(OCH2~etrahydl~ru.dl}3~1) 2 Iaa. 68 ~?(=O)(OCH2~yrrolidin 1--yl) 2 Iaa. 69 --P(=O)[OCH2{2~yrrolido~l--Yl)] 2 Iaa. 70 P(=~)(~CH2~etrallydnv~rl~2--Yl) 2 Iaa. 71 ~?(=o)(ocH2~etrallydlu~rl~3~l) 2 Taa. 72 --P(=o)(ocH2~etrally~llu~yl~yl) 2 Iaa. 73 ~(=o)(ocH2~irpn~li~l--yl) 2 Iaa. 74 --P(=O)(OCH2~noIpholin~yl) 2 25 Iaa. 75 --P(=O)(OH)(OCH3) Iaa. 76 ~?(=O)(OH~(OC2Hs) Iaa. 77 --P(=O)(OH)[O{n-C3H7)]
Iaa. 78 ~(=O)(OH)[OCH(CH3)2]
3 0 Iaa. 79 ~(=~)(~H)[~~n~4Hs)]
Iaa. 80 ~(=O)(OH)[OCH2-CH(CH3)2]
Iaa. 81 ~(=~)(~H)[~CH(CH3~C2Hs]
Iaa. 82 --P(=O)(OH)(OCH2-CF3) 3 5 Iaa. 83 ~(=O)(OH)(OCHz-CH2{)H) Iaa. 84 ~P(=O)(OH)(OCH2-CH2{~N) Iaa. 85 --P(=O)(OH)(OCH2-CH2-OCH3) Iaa. 86 ~(=O)(OH)(OCH~CH2-OC2H5) 4 0 Iaa. 87 ~(=O)(OH)(OCH2-CH2-OCF3) Iaa. 88 --P(=O)(OH)(OCH2-CH2-OCH2-CH=CH2) Iaa. 89 --P(=O)(OH)(OCH2-CH2-OCH2~ a CH) Iaa. 90 ~P(=O)(OEI)(OCH2-CH2~cyclopentyl) Iaa. 91 --P(=O)(OH)(OCH2 CH2~H2) Iaa. 92 ~P(=O)(OH)(OCH2-CH2 NH-CH3) Iaa. 93 --P(=O)(OH)[OCH2 CH2~(CH3)2]

a4 No. --p(=y)(zlRl)(z2R2) Iaa. 94 ~(=O)(OH)(OCH2-CH2~CH3) Iaa. 95 ~(=O)(OH)(OCH2-CH2~C2HS) 5 Iaa. 96 ~(=O)(OH)(OCH2-CH2~CF3) Iaa. 97 ~(=O)(OH)(OCH2-CH2~CH2-CH=CH2) Iaa. 98 ~P(=O)(OH)(OCH~CH2~CH2-C 3 CH) Iaa. 99 ~(=O)(OH)(OCH2-CH2~O-CH3) Iaa- 100 ~P(=O)(OH)(OCH2-CH2~O-C2Hs) Iaa. 101 ~P¢=O)(OH)(OCH2~02-CH3) Iaa. 102 ~P(=O)(OH)(OCH2~02-C2Hs) Iaa. 103 ~?(=O)(OH)(OCH2-CH2~Oz{~H3) Iaa. 104 ~P(=O)(OH)(OCH~CH2~02-C2H5) Iaa. 105 ~(=O)(OH)(OCH2-CH=CH2) Iaa. 106 ~P(=O)(OH)(OCH2{~H=CH-CH3) Iaa. 107 ~(=O)(OH)(OCH2-CH2-CH=CH2) 2o Iaa. 108 ~P(=O)(OH)(OCH2 CH=CH-CI) Iaa. 109 :P(=O)(OH)(OCH2-C 3 CH) Iaa. 110 ~(=O)(OH)[OCH(CH3}C--CEI~
Iaa. 111 ~(=O)(OH)(OCH2-CO-OCH3) Iaa. 112 ~(=O)(OH)(OCH2-CO-OC2Hs) Iaa. 113 ~(=O)(OH)[OCH(CH3~CO-OCH3]
Iaa. 114 ~P(=O)(OH)[OCH(CH3~CO-OC2H5]
Iaa. 115 ~(=O)(OH)(OCH2-CO~H2) 30 Iaa. 116 ~?(=O)(OH)(OCH~CO~H-CH3) Iaa. 117 ~P(=O)(OH)[OCHz-CO~(CH3)2]
Iaa. 118 ~P(=O)(OH)[OCH(CH3}CO~H2]
Iaa. 119 ~(--O)(OH)[OCH(CH3) C0~H-CH3]
3 5 Iaa. 120 3?(=O)(OH)[OCH(cH3~cO~(cH3)2]
Iaa. 121 ~(=O)(OH)(O~yelopropyl) Iaa. 122 ~(=O)(OH)(O~yclobutyl) Iaa. 123 ~(=O)(OH)(O-eyelopentyl) Iaa. 124 ~P(=O)(OH)(O-eyelohexyl) Iaa. 125 ~(=O)(OH)(OCH2~yelopropyl) Iaa. 126 ~(=O)(OH)(OCH2-eyelobutyl) Iaa. 127 ~(=O)(OH)(OCH2-eyelopentyl) Iaa. 128 ~?(=O)(OH)(OCH2-cyclohexyl) Iaa. 129 ~(=O)(OH)(O-phenyl) Iaa. 130 ~P(=O)(OH)(OCH2--phenyl) No. --P(--y)(zlRl)(z2R2) Iaa. 131 ~(=O)(OH)(O-oxetan 3--yl) Iaa. 132 ~(=O)(OH)(O~ y~ ru~}2--yl) 5 Iaa. 133 ~P(=O)(OH)(O~etraLydlurula~3--yl) Iaa. 134 ~(~O)(OH)(O~etrahydropyran 2--yl) Iaa. 135 ~(=O)(OH)(O~etraLy~ul,yl~yl) Iaa. 136 ~P(=O)(OH)(O~etrahyLupyl~n~yl) Iaa- 137 ~?(=o)(oH)(ocH2-oxiran 2--yl) Iaa. 138 ~?(=O)(OH)(OCH~oxeta~3~1) Iaa. 139 ~?(=O)(OH)(OCH2~etrahydrofilran 2--yl) Iaa. 140 ~(=O)(OH)(OCH2~etrahydrofilran 3--yl) Iaa. 141 ~(=O)(OH)(OCH2~pyrrolidi~1~1) Iaa. 142 ~(=O)(OH)[OCH2 (2--pyrrolido~l--yl)]
Iaa. 143 ~?(=O)(OH)(OCH2~e~ahydropyra~2~1) Iaa. 144 ~(=O)(OH)(OCH~tetrahydropyraI}3--yl) ao Iaa. 145 ~(=O)(OH)(OCH2 tetrallyd,~yl~yl) Iaa. 146 ~(=O)(OH)(OCH~piperidi~l--yl) Iaa. 147 ~P(=O)(OH)(OCH~norpholi~yl) Iaa. 148 ~?(=O)(OCH3)(0C2Hs) Iaa. 149 ~?(=O)(OCH3)[0~n C3H7)]
Iaa. 150 ~(=O)(OCH3)[0CH(CH3)21 Iaa. 151 ~P(=O)(OCH3)[0~n C4Hg)]
Iaa. 152 --P(=O)(OCH3)[0CH2-CH(CH3)2]
3 Iaa. 153 ~P(=O)(OCH3)[0CH(CH3}C2Hs]
Iaa. 154 --P(=O)(OCH3)(0CH2-CF3) Iaa. 155 ~(=O)(OCH3)(0CH2-CH2-OH) Iaa. 156 --P(=O)(OCH3)(0CH~CH2 CN) Iaa. 157 --P(=O)(OCH3)(0CH2-CH~OCH3) Iaa. 158 --P(=O)(OCH3)(0CH2-CH~OC2Hs) Iaa. 159 ~(=O)(OCH3)(0CH2-CH~OCF3) Iaa. 160 ~(=O)(OCH3)(0CH2-CEI~OCH2~H=CH2) Iaa. 161 --P(=O)(OCH3)(0CH2-CH~OCH~C--CH) Iaa. 162 ~?(=O)(OCH3)(0CH2-CH~cyclopentyl) Iaa. 163 ~(=O)(OCH3)(0CH2-CH~NH2) Iaa. 164 --P(=O)(OCH3)(0CH2-CH2~H-CH3) Iaa. 165 --P(=O)(OCH3)[0(: H2~CH2~(CH3)~]
Iaa. 166 --P(=O)(OCH3)(0CH2-CH2~CH3) Iaa. 167 --P(=O)(OCH3)(0CH2-CH~SC2Hs) No. _p(--y~(zlRI)(Z~R2) Iaa. 168 ~(=O)(OCH3)(0CH~CH2~CF3) Iaa. 169 --P(=O)(OCH3)(0CH2-cH~scH2-cH=cH2) 5 Iaa. 170 ~P(=O)(OCH3)(0CH~CH~SCH~C----CH) Iaa. 171 ~(=O)(OCH3)(0CH2-CH2~0-CH3) Iaa. 172 ~?(=O)(OCH3)(0CH2-CH2 SO-C2H5) Iaa. 173 ~P(=O)(OCH3)(0CH~SO~CH3) Iaa- 174 ~?(=o)(ocH3)(ocHz~o2-c2H5) Iaa. 175 --P(=O)(OCH3)(0CH2-CH~SO~CH3) Iaa. 176 ~(=O)(OCH3)(0CH~CH~O~C2Hs) Iaa. 177 --P(=O)(OCH3)(0CH~CH=CH~) Iaa. 178 ~P(=O)(OCH3)(0CH2 CH=CH--CH3) Iaa. 179 ~(=O)(OCH3)(0CH2-CH~CH=CH2) Iaa. 180 ~?(=O)(OCH3)(0CH2-CH=CH-Cl) Iaa. 181 ~P(=O)(OCH3)(0CH2-C--CH) 2 o Iaa. 182 --P(=O)(OCH3)[0CH(CH3~C--CH]
Iaa. 183 ~(=O)(OCH3)(0CH~C~OCH3) Iaa. 184 ~P(=O)(OCH3)(0CH~CO~C2H5) Iaa. 185 --P(=O)(OCH3)[0CH(CH3~CO-OCH3]
2 5 Iaa. 186 ~(=O)(OCH3)[0CH(CH3~CO-OC2Hs]
Iaa. 187 --P(=O)~ CH3)~0CH2-Co~NH2) Iaa. 188 --P(=O)(OC~3)(C~CF~CO NH--CH3) Iaa. 189 ~P(=O)(OCH3)~0CH~CO~(CH3)2]
3 0 Iaa. 190 ~(=O)(OCTsl3)[0CH(CH3~CO~H2]
Iaa. 191 ~P(=O)(OCH3)[0CH(CH3) C0~H--CH3]
Iaa. 192 ~(=O)(OCX3)[0CH(CH3~CO~(CH3) Iaa. 193 --P(=O)(OCH3)(~cyclopropyl) 3 5 Iaa. 194 --P(=O)~CCH3)(0-cyclobutyl) Iaa. 195 ~(=O)(OCH3)(~cycloperltyl) Iaa. 196 --P(=O)(OCH3)(0~yclohexyl~
Iaa. 197 --P(=O)(OCH3)(0CH~c~-clopropyl) Iaa. 198 --P(=O)(OCH3)(0CH~cyclobutyl) Iaa. 199 --P(=O)(OCE~3)~0CH~cyclopentyl) Iaa. 200 --P(=O)(OCH3)~0CH~cyclohexyl) Iaa. 201 --P(=O)(OCH3)(~pllenyl) Iaa. 202 --P(=O)(OOEI3)~0CH~phenyl) Iaa. 203 --P(=O)(OCH3)(0-oxetan 3--yl) Iaa. 204 --P(=O)(OCH3)(0-tetrahydrofilra~2--yl) No. --P(=Y)(ZlRl)(Z~R2) Iaa. 205 --P(=O)(OCH3)(0--tetrahydrofilra~3--yl) Iaa. 206 --P(=O)(OCH3)(0~etrahydropyraI}2--yl) 5 Iaa. 207 --P(=o)(ocH3)(o~tetrah~d~uyylan ~yl) Iaa. 208 --P(=O)(OCH3)(0 te~al,y&~yl~yl) Iaa. 209 --P(=O)(OCH3)(0CH~oxiraI}2~1) Iaa. 210 --P(=O)(CCH ,)(OCElT2~xeta~3--yl) 1 0 Iaa. 211 --P(=O)(OCH3)(0CH2--te~rahy.llurul~l~2--yl) Iaa. 212 ~P(=O)(OCTH3)(0CH2~etrahy~1lurul-al~yl) Iaa. 213 --P(=O)(OOE~3)(0CH2i~yrrolidi~1--yl) Iaa. 214 --P(=O)(OCH3)[0CH2~2~yrrolido~1--yl)]
Iaa. 215 --P(=O)(OCH3)(0CH2-tehahyd~ y.~2--yl) Iaa. 216 --P(=O)(OCH3)(0CH2--teh-ahydropyran 3--yl) Iaa. 217 P(=O)~OCE~3)(0CE~2 teh~hyll~u~uy~ 4 yl) Iaa. 218 :P(=O)(OCE~3)(0CH2-piperidi~l--yl) Iaa. 219 --P(=O)(OC'~3)(0CH2 molpholin~yl) Iaa. 220 --P(=O)(OC~rIs)if~f~C3H7)]
Iaa. 221 ~(=O)~OC~Hs)~OCH(CH3)~
Iaa. 222 ~(=O)(OC7Hs)~O-~f~C4Hg)]
2 5 Iaa. 223 ~P(=O)~GC~Hs)[OCH~2-CHfCH3)2]
Iaa. 224 --P(=G)(OC~Hs)[OCEI(CH3) C~Hs]
Iaa. 22S --P(=Q)(GCr~Hs)(OCEl~CF3) Iaa. 226 --P(=O)(CC~ ISY~OCH~CH2~H) Iaa. 227 ~?(=O)~OC2Hs)(OCH2-CH2 CN) Iaa. 228 --P(=0}~0C2Hs)~OCH2-CH2-OCH3) Iaa. 229 ~(=O)~CC~ s)(OCrX2 CE~OC2H5) Iaa. 230 --~(=C)(CC2'~Is)(OCIH2-CH2~CF3) 3 5 Iaa. 231 ~(=O)(CC~rdS)(OCH2--CH2--CCH2--CH=CH2) Iaa. 232 ~(=O)(OC~Hs)tOC~CH~CH~C a CH) Iaa. 233 --P(=O)(CC7Hs)~ OCH2~H2~cyclopentyl) Iaa. 234 ~(=O)(OC2Hs)~OCX2-CH2~H~) Iaa. 235 --P(=O), OC~E~s).~OCX2-CH2~H-CH3) Iaa. 236 ~(=O~CC2Hs3LOCH2~X2--N(CH3)2]
Iaa. 237 --P(=O)(CC2r~s)(3c~2-cH2~cH3) Iaa. 238 ~(=O)(CC~Hs)tOCX2-CH2~C H5) Iaa. 239 --P(=O)(CC~rHs)~'C)CH~CH2~CF3) Iaa. 240 --P(=O)(OC~Xs)r~ CX2-CH2~CH2-CH=CH2) Iaa. 241 --P(=O)(OC2Xs,(CCH2-CX2~;CH~C _ CH) -No. --P(=Y)(ZIRI)(Z2R2) Iaa. 242 --P(=O)(OC2Hs)(OCH2~H2 SO-CH3) Iaa. 243 --P(=O)(OC2Hs)~OCH2-CH~C~Hs) Iaa. 244 -~(=O)(OC2H5)(OCH2-SO~-CH3) I2a. 245 -P(=O)(OC2Hs)(OCH ~ O~-C~H5) Iaa. 246 --P(=O)(OC2Hs)(OCH~CH~SO2-CH3) Iaa. 247 -p(=o)(Gc?-rd5)(oc~ ~ n~-S~2 ~ 2H5) 10 Iaa- 248 ~(=o)~oc2Hs)l~oc~2-cF~=c~) Iaa. 249 -P(=O)(OC2H5)i~GC~2-_~'=CH-CH3) Iaa. 250 -P(=O)(OC~s)~Oc~2-cn ~ H=c~2) Iaa. 251 --c'(=O)(OC2EI5)~OCH2~'rl=CH-CI) Iaa. 252 -~(=o)(Gc2T~5)(ocrn2-c--C ~
laa. 253 --P(=O)(OC2Hs)[~CI T(CH3){~ 5 CH]
Iaa. 254 ~(=O)(C~ Hs)(OCEI~O OCH3) Iaa. 255 --P(=O)(3C~Hs)l'CCH2~O{)C2Hs) Iaa. 256 --P(=O)(OC~H5)1CCH(CH3,~,O~C',H3]
Iaa. 257 ~(=O)(OC~s)rGCH~CH3) C~OC2Hs]
Iaa. 258 ~?(=O)~OC2~s)~OCn2~H2) Iaa. 259 ~(=O)(GC2E~5)(OCH~O~'H-CH3) Iaa. 260 --~(O)(C~2~5)[0C~--2 CC~(CH3)2]

Iaa. 261 ~P(=O)(CC s)loc~cH3)~H2]
Iaa. 262 --P(=.~i(G.-~-15)rOC~(CH3)~O~NH~H3]
Iaa. 263 ~ ( ~)~OC2 ~sj GC'-- (C~3,~O N(CEI3)2 30 Iaa. 264 i?(=O)i~OC2~sj~G cyclopI~pvl?
Iaa. 265 --~(=O)(OC .-~s)(~yclo~utyl Iaa. 266 --?(=C.3(GC2rr~s)(~yclopentyl'~
Iaa. 267 ~'(=G)(Cv"2~5)(.~:yclc~hexylj Iaa. 268 --P(=vj~OC2I~r5)~.t_r~2_~clo~)r~pyl) Iaa. 269 ~'~='v')~vC2~s)~C~-r~2~tyl) Iaa. 270 ?~=O)(CC2T~5'.. ~t:iCX2~;1c.uentyl) Iaa. 271 ?(=O3~OC2I-53~CCrl2~yel~lexyl) Iaa. 272 ~'~=C)(CC2r~5)~her,yl!
Iaa. 273 --I~'~=C)(CC2~I5?~Cr~2~ther.y'.) Iaa. 274 ~(=O?(CC-,rl.5)t'~txetar~3--y 3 Iaa. 275 --r~ )3~vC 2I-Ts~tetra ~ fiu~2~l) Iaa. 276 --~(=O)~::)C2~5)(~tetrahy 'ro~u.~yl3 Iaa. 277 ~ )'vC2~I5"~C~etrahydrG~tyrar~2--yl) Iaa. 278 --r~(-O)~"C2I-l5~ tralyd.v~.yra~3--yl) - - -.

No. --P(=Y)~ZlR l)(Z~R2) Iaa. 279 l?(=O)(OC2H5)(~tetrahydropyraT~yl) Iaa. 280 ~(=O)(OC~Hs)(¢CH2~xiran--2--yl) Iaa. 28l --P(={))~OC~H5)(0CH2 oxetan 3--yl) Iaa, Z82 ~(=O)(OC2~I5)(OCH~e~rahydrofilra~2~l) Iaa. 283 --P(=O)(OC2Hs)(OCH2~etrahydrofilra~3--yl) Iaa. 284 --P(=O)~ OC ~'nT.5)~C~~n~yrrolidi~l~l) Iaa- 285 ?(=O)(~Oc2rIs)l Gc~2 - ~2~yrn)lido}~l~l)]
Iaa. 286 :P(-O)~OC2T~5',l'C,CT~I~.e~rahydropyraT~2~1) Iaa. 287 --P!-O)(CC2~s)~OC.~e~dhy~ropyra~yl) Iaa. 288 --i~(=G)~G~~2.T.~s)(o~-~2~e~r~aydropyran~yl) 15 Iaa. 289 --P(=G)(CC~T~Is~OCE~iperidi~l~l) Iaa. 290 P(=~)(O~-2~-5)~OCrI~no~pholir~l) Iaa. 291 --P(=O)(l~henyleneQioxy) Iaa. 292 --P(~-O){O CH~H~O) 2 o Iaa. 293 --P(=O), C~CH(CH3}C~Oi Iaa. 294 --?(=Oj, C~C'~(CH3}C~T(C~3'~O]
Iaa. 295 --P(=G)[G CH(CO~{CrI~) C'n(COOCH3~0]
Iaa. 296 ~?(-O)(C CH2~E~H2~)~
2 5 Iaa. 297 3?(=O)~C CH ~ ~CH3) ~ h2 ~ ]
Iaa. 298 --P(=O)(~ CI~ ~ H ~ CH ~ O) Iaa. 299 ~ ~=S)(0 ~)2 Iaa. 300 ~(=S)~J~_H~
3 0 Iaa. 301 --?(=S)(C~ ~s)2 Iaa. 302 ~ (=S)~ ~ (r.~ 3 ~2 Iaa. 303 ~ ~=S)~ ~c4'nrs)i2 Iaa. 304 --P(=S)~(}Cn ~ ~ ~ fH ~ )) 3 5 Iaa. 305 ~ ~r~2~2 Iaa. 306 ~(-3j~ n3~2 Iaa. 307 --~t[~ c-i3k3~
Iaa. 308 --~?~=Cj(I~2E~',7 Iaa. 309 --P(=C)[1~tC2~5 ~ ~ l2 Iaa. 310 -~ J)i~~r~H~'r~ x--~ ~2)2 Iaa. 311 --~ )2 Iaa. 312 ~ (~H~y- l~)orupyl)7 Iaa. 313 ~. (=C)~TH~ clopellt~l) Iaa. 314 ~ h~1,YI
Iaa. 315 --~=O)(~T~ ny No. _P(=Y)(ZIRl~Z2~2) Iaa. 316 --P(=O)(pyrrolidm I--Yl) 2 Iaa. 317 ~(=0)(2~nethox~c~rbo~ylpy~Tolidi~1--yl) 2 5 Iaa. 318 --P(=O)(NH-CHff~OCH3)2 Iaa. 319 --P(=O)[N(CH3) CH~C0 OCH3]~
Iaa. 320 --P(=O)(NH{~H~CO~C2EIs)2 Iaa. 321 ~(=O~ CF~T3) CH2{~CC2~s]2 Iaa- 322 --~(=O)[NH~'H~C~3~C0 CCH3]2 Iaa. 323 -~=OJ~OH)(r~I~
Iao~. 324 --~(=O)(CT~)~r'r~
Iaa. 325 --P(=O)(CH)~N(CH3)~j Iaa- 326 --P(=0)(~ 2~5) Iaa. 327 --P(=O)(t:)H)r~(C?.~sJ2i Iaa. 328 ~P(=O)(O.'~I)f'i~r~{~r~,~H=rH~) Iaa. 329 ~( OJ~GH)(~~~n~c a CH) 20 Iaa. 330 ~P~=O~G.Td)~,'H ciy-~k,pl-opy~) Iaa. 331 ~P(=CJ)(OEI) ~H~H~cvclopen~l) Iaa. 332 3?(=O)(O~)~ H~hen~i) Iaa. 333 --P(=O)(~A~H)~i''r~ Ei~p'nen~
2 5 Iaa. 334 ~=Oj~O~ ~}--yl) Iaa. 335 --I'(=3',(0T~ 2~ne~no~car~-)~.y~pyrrolidir~i--yl) Iaa. 336 ?(=~ C~ ~.~ffo--~ ~crI3) Iaa. 337 ?~ )(OI~)~(CTn~,~CEI~CO{~CH3]
3 0 Iaa. 338 P{ C)(CE~ N~ C~2~ C~C2Hs) Iaa. 339 ~P(=C?~ H)~ ?{ E~rff,~C2H5]
Iaa. 340 ~ (O~=~r~ ~(cr~3~o~cH3]
Iaa. 341 ~ O~ ,r~) 35 Iaa. 342 --~ CC~!~T~i~H3) Iaa. 343 --r~=~'/~C'C~-.33~'~-~3)23 Iaa. 34 T --~?~ C)(CC~ ~2~) Iaa . 345 ( C ) ( C ~_ ~.3) ~ ~ C, ~ ~ ~ ' ]
4 Iaa. 346~(=Aj~ ~C r T~lT~ =
Iaa. 347T~ CTr~ Cl~) Iaa. 348 --~=C,~ H~).''~~~y~,o~,rc,p ,11) Iaa. 349 --?(=~j'C.CH~',.NE~L-.2~1i,pen~yl) Iaa. 350--~=v ,(C~cr:~3 J~ h~f.y ) Iaa. 351 --?(=Cj(GCTH3ji~N~TrI~henyl) Iaa. 352P( v i~,~ ~3), l ly i ~ iiu ~

...,, . _ 0050/46587 CA 02245~41 1998-08-06 No. _p(=y)(z~ 2R~) Iaa. 353 --P(-O)((:~CE~3)('2~nethoxycdr~tonylpyrrolidi~l--yl) Iaa. 354 ~?(=O)(OC'~I3)(NH~H~-CO OCH3) Iaa. 355 --P(=O)(OCEi3)~NrCH33-CH~CO OCH3]
Iaa. 356 --P(=0)(3CH3)fN~H~CC~OC?Hs) Iaa. 357 ~(=O)(OCH3)~N(CH3~CH~C~OC .H5]
Iaa. 358 ~(=O)~vC~ ~ Li(CH3) CC)~)CH3]
Iaa- 359 --?(=vj(OC?~5~ 7~
Iaa. 360 ~(=C~j(G~ 2~s3~n---~3) T ~ r ~ T~ ~ T 'r ~ ~ ' '_T T ~ ~
laa. ~01 ~. ~=V~J~?~ s) ~ )?~
Iaa. 362 --P(=O)(vC?~si~N~2ns) Iaa. 363 --P~=o)(vc2~s~;N(c?Hs)?3 Iaa. 364 ~=O~¢OC2~c3~'T~--CX~H-CH2) Iaa. 365 --?~=O)i~OC?I-5j~ ~n?--C g CH) Iaa. 366 ?(=C,)(C,C?~s),~T~I~y~ ,propyl) 2o Iaa. 367 ~ J(GC?.Igs).~ . ;open~l) Iaa. 368 ~(=~'''Jl~?-~--'jt~-r-~-i~}lellYl'~
Iaa. 369 ~(=Oj(OC )~ ~n~t1l~nyl) Iaa. 370 ~'(-Ojt'OC2!rs)~yrroiidir~;~yl) 2~ Iaa. 371 ~f=Oji~C?-~s u'~ne~hoxycilrho~ylpyrrolidi~1~1) Iaa. 372 ' ~f=5j~C~C?Hrs~iH~r~C.~')CH3) Iaa. 373 ~(=C j(C~C?--s ~ H~ ?~ ~OCH3]
Iaa. 374 ?~ (C~C?.H~ l~ Ei~C& {)C2H~) Iaa. 375 ?(=~ J~-r~5)l~-lCH~)~H~CO OC2Hs]
Iaa. 376 ~ JC Ir )~ n '~{:''~OCH33 T ~ r~ r~r~r~ _ _rT ~
laa. ~ -n3 ~?~tJ~
Iaa. 378 ---~--Oj~C~3~?j;;J~ ?~5j Iaa. 379 T ~--'--'iLr~ '-T~3)?1L~ i~C3h~)3 Iaa. 380 ; ?. =O)[~, C!~ ZTA~~rn3~?;
Iaa. 381 ~ ~lc~iT~)?~ r~xs)3 Iaa. 382 --~'=O)~ C~ ,;OCA~-CH2) 0 Iaa. 383 ~=O)~(CI~3~ O"I~
Iaa. 384 --P~ r~(C~3l7jtS~ yclG.i~xyl) Iaa. 385 ~ CTl-~3)?l(~ .yl) Iaa. 386 ~=v)~;~ 3)?~ h~
Iaa. 387 j?~=O~ C,~)?J,~ f;~
Iaa. 388 ~=O ~ CX-.,?'i;}t~ a.ivl;;o.urar~2--yl) Iaa. 389 ~=Oj~ ~T~Ci,I~',~';OCl~2~x~.a~3--yl) ,2 No. --P(=Y)(~ IF~ R2) Iaa. 390 ~(=Q)~-~CH3)~OCH~CF3) Iaa. 391 ~(=O)l~-(C7~~'?1fOC--~CO OCH3) 5 Iaa. 392 ~(=O)rN(CH3)~J(OCH~CO-OC~Hs) Iaa. 393 ~(=O)(NH~h~CH~0) Iaa. 394 --P~=O)(N7H-CH~Cn~) Iaa. ~ =v) l~t~ ~3)~_~n~~ ~n3)J
1 0 Iaa. 3 96 Iaa. 397 ?(=~j~'r~H~h~rI~'~Hj Iaa. 398 ~ O)~ H3~ rlffr~2~~r~L~i(CH3j]
Iaa. 399 7 I'=~)rc3--Cn~--~ Cr~3) ~,h ~ ]
400 ?~ O)~H C~C ,~ ~ h~(CH3)]
Iaa. 40 1 ~?~ O)~ 7T ~T~T~'~ rh?~ H 2--N(CH3)]
Iaa. 402 ---?~ r~ ~T~~r~ 7?--~7n7-~]
Iaa. 403 ~ r~H?~H?~ ?--~]
2 0 Iaa. 404 ~=.,)r~, A~ ~
Iaa. 405 ~(=S)~,TE~rt~ ~3'~?
Iaa. 406 ~.~=S) j ~(CH3h]2 Iaa. 407 ( S)(N~?rl~)?
a5 Iaa. 408 ?t'=S)~T~C~s)7i?.
Iaa. 409 ~'=S)~',T~T~--_h~J~,~--r~2 Iaa. 41 n - ?~ A~r~?~rr~?iyT~) Iaa. 411 ''( ~)r T(C~, ~Cn~2~H?~(~,H3)3 Iaa. 412 ?,~=vJ(SCn3j?.
Iaa. 413 ~~~'={;)~'SC2Hs ~~, Iaa. 414 '~~~=v;~ ;~3n~jl2 Iaa. 41~ --?~ ) S~ C~3~., 35 Iaa. 416 --~ J)rs - ~t'an~j3~ _ Iaa. 417 '?~ )J~t_ri?~Tr--~_~? n Iaa. 418 ; ~- =v~t'~L~I~ylj?
Iaa. 419 ~ CE~ c~;)_ T A ~~ ' r T .~
laa. LT ~ U ~-- I--v~ n?--~--~J~_n 3;_ Iaa. 421 ~ 3- S~ V~ 3_ Iaa. 422 ~ ~)(S~ ?~lT?~ ~
Iaa. 423 ?.--3.. S~,~ ?.~.~~--vj Iaa. 424 '--~-',=3~C~
Iaa. 425 ?~ =3)(~C.?E~J?
Iaa. 42~ , =S)~r;'~(~ 3 ~7')l_ No. --p(=Y)i~!RI)~Z7R~) Iaa. 427 ~(=S) ~C~,Hg)]~
Iaa.. 428 ~(=S)(~CHrCH~H~S) 5 Iaa. 42~ =S)(S CH~CE~:~H~O) . 30 _ Furthermore, the following substituted 2-phenylpyridines of the formulae Ia~-Ioy are especially preferred, in particular 5 - the compounds Ia~.l - Ia~.429, which differ from the corre-sponding compounds Iaa.l - Iaa.429 only by the fact that R4 is chlorine:

Cl ~ CH2 z2R2 Ia~
N

F3C zlRl 15 - the compounds Iay.l - Iay.429, which differ from the correspond-ing compounds Iaa.l - Iaa.429 only by the fact that R4 is fluo-rine:
F Cl Fl ~ Y
~N CH2 ~ z2R2 Iay F3C zlRl 25 - the compounds Iba.l - Iba.429, which differ from the corre-sponding compounds Iaa.l - Iaa.429 only by the fact that X is 1,2-ethanediyl:

Cl ~ CH2 - CH2 ~ z2R2 - the compounds Ib~.l - Ib~.429, which differ from the corre-spon~; ng compounds Iaa.l - Iaa.429 only by the fact that X is 1,2-ethanediyl and R~ is chlorine:

Cl Cl Cl ~ CH2 CH2 . ' Z2R2 N

0050/46587 CA 0224554l l998-08-06 - the compounds Iby.l - Iby.429, which differ from the correspond-ing compounds Iaa.l - Iaa.429 only by the fact that X is 1,2-ethanediyl and R4 is fluorine:

~ N CH - CH I - Z2R2 Y
F3C zlRl - the compounds Ica.l - Ica.429, which differ from the corre-sponding compounds Iaa.l - Iaa.429 only by the fact that X is -CH2-CH(Cl)- :
Cl ,~J~ CH2 C~ ' z2R2 N

F3C ~lRl - the compounds Ic~.l - Ic~.429, which differ from the corre-sponding compounds Iaa.l - Iaa.429 only by the fact that X is -CH2-CH(Cl)- and R4 is chlorine:

Cl ~ CHa CE: - ~ Z2R2 F3C ~lRl - the compounds Icy.l - Icy.429, which differ from the correspond-ing compounds Iaa.l - Iaa.429 only by the fact that X is -CH2-CH(Cl)- and R4 is fluorine:

~ ~ CH~ C~ Z2R2 Y
N

F3C zlRl - the compounds Ida.l - Ida.429, which differ from the corre-sponding compounds Iaa.l - Iaa.429 only by the fact that X is -CH2-CH(Br)- :

_ 0050/46587 CA 0224554l 1998-08-06 Cl ~ CH2 CH z2R2 N
F3C ~lRl - the compounds Id~ Id~.429, which differ from the corre-spon~; n~ compounds Iaa.1 - Iaa.429 only by the fact that X is -CH2-CH~sr)- and R4 is chlorine:

Cl Cl Cl ~ sr Y
15 ~ CH2 CH Z2R2 N

F3C zlRl - the compounds Idy.1 - Idy.429, which differ from the correspond-ing compounds Iaa.1 - Iaa.429 only by the fact that X is -CH2-CH(Br)- and R4 is fluorine:

~ CH2 - CH P z2R2 N

F3C ~lRl 30 - the compounds Iea.1 - Iea.429, which differ from the corre-spo~1ng compounds Iaa.1 - Iaa.429 only by the ~act that X is -CH2-CH(CH3)- :

~ ~ CH2 CH ~ 2 2 Iea N

- the compounds Ie~.1 - Ie~.429, which differ from the corre-~ponding compounds Iaa.1 - Iaa.429 only by the fact that X is -CH2-CH(CH3)- and R4 is chlorine:

_ -0050/46587 CA 0224554l l998-08-06 Cl CH~ CN ~ - z2R2 N
F3C ~lRl - the compounds Iey.l - Iey.429, which differ from the correspond-ing compounas Iaa .1 - Iaa. 429 only by the fact that X i5 -CH2-CH(CH3)- and R4 is fluorine:

Cl ~ Cl CH3 Y

~ CH2 CH zaR2 N

F3C ~lRl - the compounds Ifa.l - Ifa.429, which differ from the corre-sponding compounds Iaa.l - Iaa.429 only by the fact that X i5 -CH2-CH(CN)- :

Cl ~ CH2- CH P - z2R2 N

F3C zlRl 30 - the compounds If~.l - If~.429, which differ from the corre-sponding compounds Iaa.l - Iaa.429 only by the fact that X is -CH2-CH(CN)- and R4 i5 chlorine:

Cl ~ Cl CN y If~

CH2- CH ~ z2R2 ~'~N

- the compounds Ify.l - Ify.429, which dif$er from the correspond-ing compounds Iaa.l - Iaa.429 only by the fact that X is -CH2-CH(CN)- and R4 is fluorine:

_ ~ CH2 CH Z2R2 N
P3C ~1R1 - the compounds Iga. 1 - Iga. 429 which differ from the corre-SPOn~; ng compounds Iaa.1 - Iaa.g29 only by the fact that X i8 10 - CHa - CH ( COOCH3 ) -~ CH2 I H Z2R2 F3C ~1R1 - the compound~ Ig~.1 - Ig~.429, which differ from the corre-sponding compounds Iaa.1 - Iaa.429 only by the fact that X is -CH2 -CH (COOCH3) - and R4 i~ chlorine:

a5 ~ ' CH~ I E 2 Ig~
F3C ~1R1 30 - the compound~ Igy.1 - Igy. 429 which di~fer from the correspond-ing compound~ Iaa.1 - Iaa. 429 only by the fact that X is -CH2-CH(COOCH3)- and R4 is fluorine:

CH2 CH --~ Z2R2 N

- the compounds Iha.1 - Iha.429, which differ from the corre-~ponding compounds Iaa.1 - Iaa.429 only by the fact that X is ethene-1,2-diyl:

_ _ _ _ _ _ ~ ~ CH - CH z2R2 N
F3C ~lRl - the compounds Ih~ Ih~.429, which differ from the corre-sponding compounds Iaa.l - Iaa.429 only by the ~act that X i8 ethene-l,2-diyl and R4 is chlorine:

~ CH Z2R2 F3C ~lRl - the compounds Ihy.l - Ihy.429, which differ from the correspond-ing compounds Iaa.l - Iaa.429 only by the fact that X is ethene-l,2-diyl and R~ is fluorine:

a5 ~ CH CH - ~ z2R2 N

F3C ~lRl 30 - the compounds Iia.l - Iia.429, which differ from the corre-spO~; ng compounds Iaa.l - Iaa.429 only by the fact that X is -CH=C (Cl) ~:

Cl ~ ClH C - ~ z2R2 N

- the compounds Ii~ .429, which differ from the corre-sponding compounds Iaa.l - Iaa.429 only by the fact that X is -CH=C(Cl)- and R4 is chlorine:

0050/46587 CA 0224554l l998-08-06 Cl~CH = C _-_ZZR2 N
F3C zlRl - the compounds Iiy.l - Iiy.429, which differ from the correspond-ing compounds Iaa.1 - Iaa.429 only by the fact that X is -CH=C(Cl)- and R4 is fluorine:

15 Cl ~ CH - C z2R2 Y
N

F3C ~lRl - the compounds Ija.1 - Ija.429, which differ from the corre-sponding compounds Iaa.1 - Iaa.429 only by the fact that X is -CH=C(sr)- :

~ I p 2 2 Ija N

F3C zlRl 30 - the compounds Ij~.1 - Ij~.429, which differ from the corre-sponding compounds Iaa.1 - Iaa.429 only by the fact that X is -CH=C(Br)- and R4 is chlorine:

~ CH ~ C ~ z2R2 - the compounds Ijy.1 - Ijy.429, which differ from the correspond-ing compounds Iaa.1 - Iaa.429 only by the fact that X is -CH=C(Br)- and R4 is fluorine:

0050/46587 CA 0224554l l998-08-06 Cl ~ Cl Br y ~ CH C ~ z2R2 jY
N
F3C zlRl - the compounds Ika.l - Ika.429, which differ from the corre-sponding compounds Iaa.l - Iaa.429 only by the fact that X is -CH=C(CH3)- :

Cl ~ Cl CH3 y ~ CH C ? z2R2 N

F3C ~lRl - the compounds Ik~.l - Ik~.429, which di~fer ~rom the corre-ao sponding compounds Iaa.l - Iaa.429 only by the fact that X i5 -CH=C(CH3)- and R4 i5 chlorine:

~ CH I Ik~
N

F3C zlRl 30 - the compounds Iky.l - Iky.429, which differ from the correspond-ing compounds Iaa.l - Iaa.429 only by the fact that X is -CH=C(CH3)- and R4 is fluorine:

F Cl ~ CH - C - ~ z2R2 Iky - the compounds Ila.l - Ila.429, which differ from the corre-sponding compounds Iaa.l - Iaa.429 only by the fact that X is -CH=C(CN)- :

Cl ~J~CH-- C--~ z2R2 Ila F3C zlRl - the compounds Il~ .429, which differ from the corre-sponding compounds Iaa.l - Iaa.429 only by the fact that X is 10 -CH=C (CN) - and R4 is chlorine:

Cl Cl ~3~ CH - C--'~ z2R2 Il~
N

F3C zlRl - the compounds Ily.1 - Ily.429, which differ from the correspond-ing compounds Iaa.1 - Iaa.429 only by the fact that X is -CH=C (CN) - and R4 is fluorine:

a5 ,L~ ~ CH - C --~ z2R2 Ily N

F3C zlRl 30 - the compounds Ima.1 - Ima.429, which di~fer from the corre-8pOP~; ng compounds Iaa.1 - Iaa.429 only by the fact that X i5 -CH=C (COOCH3)--Cl ~ CH-- C--~ z2R2 N

- the compounds Im~.1 - Im~.429, which differ from the corre-sponding compounds Iaa.l - Iaa.429 only by the fact that X is -CH=C (COOCH3) - and R4 is chlorine:

0050/46587 CA 0224554l l998-08-06 .

Cl Cl Cl ~ CO Y Im~

~ N CH C ~ z2R2 F3C ~lRl - the compounds Imy.l - Imy.429, which differ ~rom the correspond-ing compounds Iaa.l - Iaa.429 only by the fact that X is -CH=C(COOCH3)- and R4 is fluorine:

F Cl ~ ~ f o Y
I l CH C ~ z2R2 ~N
F3C ~JlRl - the compounds Ina.l - Ina.429, which differ from the corre-ao sponding compounds Iaa.l - Iaa.429 only by the fact that X is - CH-OCH2- : .

~3 ~}~2--~ CH2 ~--Z2R2 N

F3C zlRl 30 - the compounds In~.l - In~.429, which differ from the corre-sponding compounds Iaa.l - Iaa.429 only by the fact that X is -CH-OCHa- and R4 is chlorine:

Cl Cl J~CH2 ~ CHa '--Z2R2 N

- the compounds Iny.l - Iny.429, which differ ~rom the correspond-ing compounds Iaa.l - Iaa.429 only by the fact that X is -CH-OCH2- and R4 is fluorine:

0050/46587 CA 0224554l l998-08-06 S ~ C~2 ~ CH2 ~ Z2R2 Iny F3C zlRl - the compounds Ioa.1 - Ioa.429, which differ from the corre-sponding compounds Iaa.1 - Iaa.429 only by the fact that X is -0CH2- :

~ ~ Cl y Ioa ~ CH2 ~ z2R2 ~i~N
F3C zlRl - the compounds Io~ Io~.429, which differ from the corre-spon~i ng compounds Iaa.1 - Iaa.429 only by the fact that X iB
-OCHa- and R4 is chlorine:

Cl Cl Cl ~ y N

. F3C zlRl 30 - the compounds Ioy.1 - Ioy.429, which differ from the correspond-ing compounds Iaa.1 - Iaa.429 only by the fact that X is -OCH2-and R4 is fluorine:

Cl ~ O CH ~ Z2R2 ~Y
N

The substituted 2-phenylpyridines of the formula I are accessible in various ways, in particular by one of the following processes:
A) By linking the phosphonyl group with the phenylpyridine moiety A.1) by diazotizing 3-pyridylanilines II and reacting the 0050/46587 CA 0224~4l l998-08-06 resulting diazonium salts with vinyl- or alkynylphosphonic acid derivatives III by the method of Meerwein {cf., for example, Org. Reactions 11, (1960), chapter 3, pp. 18g-260 and Kogyo Kagaku Zasshi 67(12), (1964), 2093-2095}:

. ~ r y diazotization l ll (copper salt)y Ar CH2 CH - ~' Z2R2 + H2C CH ? z2R2 I X = CH2CHCl, CH2CHBr~
IIIa ~lRl ~ r y diazotization l l ArNHa Ar CH = C ~ z2R2 (copper salt)y lRl + HC =~ I I ~X = CE = CCl, CH = CBr~
ao / IIIb ZlRl Ar =

\ R6 (~?n In this method, the 3-pyridylaniline of the formula II, which is either known from the literature or can be pre-pared similarly to anilines known from the literature, is first converted in a manner known per se to give the corre-sponding diazonium cation, and this is then reacted fully with IIIa or IIIb in the presence of a copper salt.

The diazonium salt is generally obtained by reacting the 3-pyridylaniline II with a nitrite such as sodium nitrite and potassium nitrite in an aqueous solution of an acid, e.g. in agueous hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid or tetrafluoroboric acid.
The nitrite is normally employed in approximately eguimolar amounts or in an excess of up to approximately five times the molar amount based on the amount of 3-pyridylaniline II.
The resulting solution of the diazonium salt, or the diazo-nium salt isolated therefrom, is then reacted with a solu-tion or suspension of the vinyl- or alkynylphosphonic acid _ _ -0050/46587 CA 0224~41 1998-08-06 derivative IIIa/IIIb in the presence of a copper salt such as coppertI) bromide, copper(II) bromide, copper~I) chlo-ride and copper(II) chloride.
Examples o~ suitable solvents are water, acetonitrile, ketones such as acetone, diethyl ketone and methyl ethyl ketone, ethers such as diethyl ether and tetrahydrofuran, and furthermore alcohols such as methanol or ethanol.
Normally, the vinyl- or alkynylphosphphonic acid deriva-tives IIIa/IIIb and the copper halide are used in approxi-mately e~uimolar amounts or in an excess of up to approxi-mately thirty times the molar amount, based on the 3-pyri-dylaniline II. However, the copper halide can also be employed in smaller or catalytic amounts.
In general, the diazotization and reaction of the diazonium salt with IIIa/IIIb are carried out at from (-100) to 50~C, preferably (-20) to +30~C.
One process variant consists in adding a nitrous ester such as tert-butyl nitrite and isopentyl nitrite, to a solution or suspension of the 3-pyridylaniline II, of the vinyl- or alkynylphosphonic acid derivative IIIa/IIIb and of the cop-per halide in an agueous system, e.g. in glacial acetic acid/hydrogen chloride, absolute methanol or ethanol, in an ether such as tetrahydrofuran and dioxane or in acetoni-trile or acetone. What has been said above for the reaction temperature and the proportions of the reactants also applies here.
A.2) by a Heck reaction (see, for example, A. surini, S. Cacchi, P. Pace, B.R. Pietroni, Synlett 1995, 677):

_ Ra ~ Ra y Ar ~Br + H2C= C !~ Z2R2 cat ; Ar- CH = C ~ z2R2 ~O - SO2CF3 zlRl zlRl IV V I~Ra = H,CN,halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, (C1-C4-alkoxy)-carbonyl, di(C1-C4-alkyl)-amino Regarding the definition of Ar, see process A.1);
cat. is a transition metal catalyst, preferably a palla-dium(II) compound such as palladium acetate.
In general, the reaction is carried out in an inert organic solvent, in particular in dimethylformamide or tetrahydro-furan.
Examples of suitable bases are carbonates ~uch as potassium carbonate, acetates such as sodium acetate and tertiary amines such as triethylamine.
The reaction is generally carried out at from 0~C to the boiling point of the reaction mixture, preferably at 50 to 10 0~C .
A.3) by Knoevenagel c~n~n~ation of aromatic aldehydes VIa or ketones VIb with phosphonic acid derivatives VII:

Ar- CHO ~VIa) ~ + Rb CH2 ' z2R2~cat.
C0 (Cl-C~-alkyl) ~1R1 VII H ~ 1 I
I Ar C - C f~ Z2R2 Rb zlRl .

-0050/46587 CA 0224~4l l998-08-06 As regards the definition of Ar, see process A.1);
Rb is cyano, Cl-C4-alkoxy or (C1-C4-alkoxy)carbonyl;
cat. is a catalyst, e.g. piperidine~acetic acid, sodium methoxide, sodium ethoxide, titanium tetrachloride/
N-methylmorpholine, or chlorotri(isopropoxy)titanium/
triethylamine.
The process is normally carried out in an inert organic solvent, e.~. in an aromatic hydrocarbon such as toluene, a lower alcohol such as methanol and ethanol or in a chlori-nated hydrocarbon such as dichloromethane.
The reaction temperature is generally ~rom 0~C to the boil-ing point o~ the reaction mixture.
The water which is liberated during the reaction can be removed by means of azeotropic distillation, if so desired.
In this case, the process is preferably carried out in an aromatic hydrocarbon such as benzene, toluene and the xylenes at the particular boiling point o~ the reaction mixture {see, for example, S. Abdallah-El Ayoubi, F. Texier-Boullet, J. Hamelin, Synthesis 1994, 258;
D. Danion, R. Carrie, Tetrahedron Lett. 1968, 4537;
F. Texier-Boullet, A. Foucaud, Tetrahedron Lett. ~1 (1980) 2161; S. Patai, A. Schwartz, J. Org. Chem. ~ (1960), 1232;
J.M. McIntosh, R.A. Sieler, Can. J. Chem. 56 (1978) 226;
M.T. Reetz, R. Peter, M. v. Itzstein, Chem. Ber. 12Q (1987) 121; K.A. Petrov, V.A. Chauzov, S.V. Aga~onov, N.V. Pazhit-nova, J. Gen. Chem. USSR 50 (1980) 1225}.
Those aromatic aldehydes VIa or ketones VIb which are not already known can be prepared in a manner known per se.
A.4) by Wittig-Horner olefination {cf., for example, B.M.G.T. Lowen, M.R. Alm~, J. Org. Chem 59 (1994) 4548;
P. Teulade, P. Savignac, E.E. Aboujaoude, S. Li~tge, N. Collignon, J. Organomet. Chem. 304 (1986) 283;
G.M. Parratt, J. Chem. Soc., Perkin Trans. 1 (1986), 1417;
B. Costisella, I. Keitel H. Gross, Tetrahedron 37 (1981) 1227}:

Ar CHO (VIa) /~
Ar CO (Cl-C4-alkyl) VIb ~ R ~_lR

H/C1-C4-alkyl y Ar C = C - n_ Z2R2 RC ~,lRl As regards the definition of Ar, see process A.1);
RC is hy~rogen, halogen, C1-C4-alkyl or di(C1-C4-al-kyl)amino.
The process is normally carried out in an inert organic 801vent, e.g. in an aromatic hydrocarbon such as toluene, a halogenated hydrocarbon such as dichloromethane or an ether such as diethyl ether, tetrahydrofuran, dioxane and 1,2-dimethoxyethane.
The anion VIII can be obtained, for example, by deprotonat-ing the correspo~; ng methanediphosphonic acid derivative with a strong base such as lithium diisopropylamide, sodium hydride and n-butyllithium.
The reaction is generally carried out at from (-100)~C to the boiling point of the reaction mixture, preferably at (-78) to +30~C.
A.5) by Wittig olefination {see, in this context, for example GB-A 12 43 214}:
~ Y
Ar - CHO (VIa) ll ' ~ Ph3P = CH P Z2R2 Ar - CO (C1-C4-alkyl) VIb ~ Z1R
IX
H/C1-C4-alkyl Ar C = CH ~ z2R2 I z As regards the definition of Ar, see process A.1);

Ph is the phenyl group.
The process is normally carried out in an inert organic solvent, e.g. in an aromatic hydrocarbon such as toluene, a halogenatea hydrocarbon such as dichloromethane or an ether such as diethyl ether, tetrahydrofuran, dioxane and 1,2-di-methoxyethane.
The reaction is generally carried out at ~rom (-100)~C to the boiling point of the reaction ~ixture, preferably at 20 to 60~C.
A.6) by Peterson olefination {see, in this context, for example O.I. Kolodyazhnyi, D.B. Golokhov, J. Gen. Chem. USSR 57 (1987) 2353; F.A. Carey, A.S. Court, J. Org. Chem. 37 (1972) 939}:

Ar-CHO (VIa) H/Cl-C4-alkyl 20 Ar-CO -alkyl ~ (VIb) ¦ ~r Ar-CO -haloalkyl*) (VIc) (H3C)3Si CH ~ z2R2 Ar-CO -dialkyl*)amino (VId) X Z
~5 strong ~ base H/C1-C4-alkyl ~ ~Ir Ar C C r z2R2 ~ I ZlRl 35 *)in each case C1-C4 H/alkyl~) haloalkyl~) I
dialkyl*)amino 40 The reaction is normally carried out in an inert organic solvent, e.g. in an aromatic hydrocarbon such as toluene or an ether such as diethyl ether, tetrahydrofuran, dioxane and 1,2-dimethoxyethane.
45 Examples of suitable strong bases are lithium diisopropyl-amide, sodium hydride or butyllithium.

-0050/46587 CA 0224~4l l998-08-06 The reaction i5 generally carried out at from (-100)~C to the boiling point of the reaction mixture, preferably at (-70) to +30~C.
Those aromatic aldehydes VIa, ketones VIb and VIc and the N,N-dialkylbenzamides VId which are not already known can be prepared in a manner known ~er se.
A.7) by coupling a styryl halide XI with a trialkyl phosphite XII or a dialkyl phosphite XIII {cf. in this context, for example, R.S. Gross, S. Mehdi, J.R. McCarthy, Tetrahedron Lett. 34 (1993) 7197; G. Axelrad, S. Laosooksathit, R. Engel, J. Org. Chem. 46 (1981) 5200}:

P[O(Cl-C4-alkyl)]3 Br XII
Ar IC =IC I or Ra Re HPO[O(Cl-C4-alkyl)]
XI
XIII

o Ar C - f - ' O(C1-C4-alkyl) Rd Re O(C1-C4-alkyl) I (y~zl~z2 = o) As regards the definition of Ar, see process A.1);
Rd,Re are hydrogen, halogen or C1-C4-alkyl.
The process is normally carried out in an inert organic solvent, preferably in an aromatic hydrocarbon such as tol-uene or an ether such as tetrahydro~uran.
The reaction of XI with a trialkyl phosphite XII is advan-tageousl~ carried out in the presence of copper(I) bromide or copper(I) chloride.
The reaction of XI with a dialkyl phosphite XIII is advan-tageously carried out in the presence of a transition metal catalyst, preferably a palladium(II) compound such as dich-lorobis(triphenylphosphine)palladium, and, if desired, in the presence of a base, e.g. triethylamine.

0050/46587 CA 0224554l l998-08-06 The reaction is generally carried out at from (-100)~C to the boiling point of the reaction mixture, preferably at approximately +25~C.

Those styryl halides XI and those phosphorus compounds XII
and XIII which are not already known can be prepared in a manner known per se.
10 A.8) by reacting a phenylacetylene XIV
- with a trialkyl phosphite XII or -- in succession with phosphorus pentachloride and an alcohol, mercaptan or amine (HZlRl/HZ2R2) in the presence of a base {cf ., in this context, for example C.E. Griffin, T.D. Mitchell, J. Org. Chem. 30 (1965) 1935; A. Meisters, J.M. Swan, Aust. J. Chem. 1~ (1965) 155; L. Maier, Synth.
Inorg. Met. Org. Chem. 3 (1973) 329; A.A. Petrov, J. Gen.
Chem. USSR ~L (1971) 1670}:

Ar C _ C H ~ XII or or 1) PCls Ar C_ C--Cl-C4-alkyl 2~ HZlRl/
XIV

~, P(0)~:)(Cl-C4-alkyl~
Ar--C IC-- P(O) (ZlRl) (Z2R2) I ~X = ethenediyl, H/Cl-C4-alkyl ( chloroethenediyl 3 As regards the definition of Ar, see process A.l).
The reaction of XIV with XII is preferably carried out in the absence of a solvent at from 20~C to the boiling point of the trialkyl phosphite XII, in particular at the boiling point of the reaction mixture.
Bases which are suitable in the reaction of the phenyl--acetylene XIV with PCls and (HZlRl/HZ2R2) are, in particu-lar, tertiary amines such as pyridine and triethylamine.~5 The reaction of XIV with PCls is preferably carried out at from 50 to 200~C, the subsequent reaction with .

0050/46587 CA 0224554l l998-08-06 (HZ1R1/HZ2R2), in contrast, at from (-100)~C to the boiling point of the reaction mixture.
Those phenylacetylenes XIV and alcohols, mercaptans and amines (HZ1Rl/HZ2R2) which are not already known can be pre-pared in a manner known per se.
A.9) by react~nq benzylidenetriphenylphosphoranes XV with a per-fluoroalk~nec~rhoxylic anhydride and subseguently with a lithium dialkyl phosphite in a manner known per se {cf. in this context, for example, Y. Shen, Q. Liao, W. Qiu, J.
Chem. Soc., Perkin Trans 1, 695 (1990)}:

15 P(Ph)3 (F3C-C02)0~ lithium dialkyl ) ~ H or (F3C-CF2-CO)2O phosphit \
Ar ~C1-C4-alkyl XV H/Cl-C4-alkyl O
Ar - C - IC P O(C1-C4-alkyl) O (Cl-C~,-alkyl) I~Y,z1,z2 = O~ CF3/C2F5 As regards the definition of Ar, see process A.1);
Ph is the phenyl group.
Those benzylidenetriphenylphosphoranes XV which are not already known can be prepared in a m~nn~r known per se.
A.10) by alkylating a phosphonic acid derivative XVI in a m~nn~
known per se using a 3-pyridylbenzyl halide XVII in the presence of a strong base {cf. in this context, for exam-ple, G.M. Blackburn, M.J. Parratt, J. Chem. Soc., Perkin Trans 1, 1425 (1986); G.M. Kosolapoff, J.S. Powell, J. Am.
Chem. Soc. 72 (1950) 4198; R.M. Keenan et al., J. Med.
Chem. 35 (1992) 38S8; H. Ahlbrecht, W. Farnung, Synthesis, 336 (1977); E. D'Incan, J. Seyden-Penne, Synthesis, 516 (1975); S. Hanessian, Y.L. B~nn~n;, D. Delorme, Tetrahedron Lett. 31 (1990) 6461~:

0050/46587 CA 0224554l l998-08-06 y Ar CH2 ~Br + Rf - CH2 ~ z2R2 strong XVII XVI ~lR

Rf Y
I~X= ethanediyl; or ethanediyl l ll which is substituted by Ar CH2 CH- P z2R2 cyano, halogen, Cl-C4-alkyl, ll 1 (C1-C4-alkoxy)carbonyl or Z R
di(C1-C4-alkyl)amino ~

As regards the definition of Ar, see process A.1);
Rf is hydrogen, cyano, halogen, Cl-C4-alkyl, (C1-C4-alkoxy)carbonyl or di(Cl-C4-alkyl)amino.
Examples of suitable strong bases are sodium hydroxide, ao butyllithium and lithium diisopropylamide.
The process is normally carried out in an inert organic solvent, preferably in an aromatic hydrocarbon such as tol-uene~or a cyclic ether such as tetrahydrofuran.
In general, the process is carried out at from (-100)~C to the boiling point of the reaction mixture, preferably from (-78)~C to +25~C.
Those phosphonic acid derivatives XVI and those benzyl halides XVII which are not already known can be prepared in a manner known per se.
A.11) by reacting aldehydes XVIIIa/XVIIIb with dialkyl phosphites XIII, if desired in the presence of ammonia or a primary or secondary amine {cf. in this context, for example, M.E. ~h~lmers~ G.M. Kosolapoff, J. Am. Chem. Soc. 75 (1953) S278; C. Li, C. Yuan, Tetrahedron Lett. 4 (1993) 1515}:
OH O
Ar- CHO (XVIIIa) XIII ~ Ar 1H n O (Cl-C4-alkyl) O (Cl-C4-alkyl) I ~X = hydroxymethylen~

0050/46587 CA 0224~4l l998-08-06 OH O
Ar-X'-CHO(XVIIIb) XIII ~ Ar X' CH - ~--O(Cl-C4-alkyl) C(Cl-C4-alkyl) I ~X = -X'-CH(OH)-~

I NH3/NH2(Cl-C4-alkYl)~ Ar CH ~----O(Cl-C4-alkyl) NH(cl-c4-alkyl)2 (H/Cl-CD,-alkyl) 2N O (Cl-C4-alkyl) I ~ X = ~m;n~methylene, Cl-C4-alkyl ~m; nomethylene or di(Cl-C4-alkyl) ~m; nomethyl ene~

20 ( 1k 1) ~
XVIIIb+XIII NH(/C C alk4yl) Y3 hr X ~ fH - ~ O(Cl-C4-alkyl) (H/cl-c4-alkyl)2N O(Cl-C4-alkyl) a5 ~ X =-X'-CH(NH2)-~
I ~ -X'-CHtNH(Cl-C4-alkyl]-,, - x~-cHtN(cl-c4-alkyl)2]-J

As regards the definition of Ar, see process A.l);
X' is unsubstituted or substituted -CH2-~ -CH2CH2-~
-OCH2- or -SCH2-, substituents which are possible being the same as in the corresponding me~n;ngS of X.
Examples of suitable solvents are water, the lower alcohols such as methanol, ethers such as tetrahydrofuran and diethyl ether, and also pyridine.
In general, the process is carried out at from (-100)~C to the boiling point of the reaction mixture, preferably from 20 to 50~C.
Those aldehydes XVIIIa/XVIIIb which are not already known can be prepared in a manner known per se.

0050/46587 CA 0224554l l998-08-06 A.12) by reacting alkyl halides XVII or XIX with trialkyl phos-phites XII in a ~nn~ known per se by the method of Arbuzov {see in this context, for example, A.Y. Garner, E.C. Chapin, P.M. Scanlon, J. Org. Chem. 24 (1959) 532;
A.G. Schultz, J.J. Napier, R. Ravic~n~an, J. Org. Chem.
(19ô3) 3408; Y. Vo-Quang, D. Carniato, L. Vo-Quang, F. Le Goffic, J. Chem. Soc., Chem. Commun., 1505 (1983)}:

Ar CH2 ~Br + XII; I ~X - CHa; y, zl, z2 =
XVII

Ar- X'' - ~Br + XII~ Ar - X'' ~ O(C1-C4-alkyl) ( I
XIX O(C1-C4-alkyl~
I ~Y,Zl,z2 = O~

ao As regards the definition of Ar, see process A.1);
X'' is, in this context, -OCH2-, -SCH2- or -Q-CH2- where Q = unsubstituted or substituted methylene, 1,2-eth~ne~;yl, oxymethylene, thiamethylene, methyle-neoxy or methylenethia.
The reaction is preferably carried out in the absence of a solvent, at from 0~C to the boiling point of the trialkyl phosphite XII, preferably from 20 to 150~C.
Those alkyl halides XIX which are not already known can be prepared in a manner known per se.
A.13) by nucleophilic substitution reaction on phosphonic acid derivatives XXI in the presence of a base ~cf. in this con-text, for example, J.L. Kelley, J.A. Linn, E.W. McLean, J.V. Tuttle, J. Med. Chem. 36 (1993) 3455}:

XXa , + L CHa P--Z2R2 ; Ar -(~) CH2 1I Z2R2 XXb I ~X= -OCH2-,-SCH2-~45 As regards the definition of Ar, see process A.1);

0050/46587 CA 0224~s4l l998-08-06 L is halogen or a customary leaving group such as methylsulfonyloxy or 4-tolylsulfonyloxy.
The process is normally carried out in an inert organic solvent, preferably in pyridine, a ketone such as acetone, or in an ether such as tetrahydrofuran.
Examples of suitable bases are butyllithium and alkali metal hydrides such as sodium hydride or alkali metal carbonates such as potassium carbonate.
In general, the process is carried out at from (-100)~C to the boiling point of the reaction mixture, preferably from 20 to 50~C.
A further possibility of synthesizing compounds I by means of a nucleophilic substitution reaction is to react 3-pyridyl-benzyl halides XVII with phosphonic acid derivatives XXII in a m~nner known per se in the presence of a base {see in this context, in addition to the abovementioned references, also S. Jarosz, E. Koslowska, Z. Ciunik, Pol. J. Chem. ~8 (1994) 2209}:

Ar CH~ ~ Br ~ } CH ~ zaR2 base XVII I l ~1R
H/alkyl~
~)alkoxycarbonyl XXII
Ar CHa (~) CH - ~ z2R2 -~ l 35 ~) in each case C1-C~ H/âlkyl~)/
~)alkoxycarbonyl I

As regards Ar, solvent, base and reaction temperature, ref-erence may be made to the above information on the reaction of XX with XXI.
Those phenols XXa and thiophenols XXb, those phosphonic acid derivatives XXI, those benzyl halides XVII and those phosphonic acid derivatives XXII which are not already known can be prepared in a manner known per se.

-0050/46587 CA 0224~s4l l998-08-06 A.1~) by reacting a phenol XXa with a halomethyl thioether XXIII
in the presence of a base, halogenolytic cleavage of the resulting alkyl thioalkyl ether XXIV, followed by an Arbuzov reaction:
Cl ~ base ArOH + Br - CH SRh ~ Ar OCH SRh I l l Rg Rg 10 XXa XXIII XXIV
(halogen)2 , ~ + XII ~Cl I X = OCH - ; ~ Ar OCH ~Br Rg Rg y zl, Z2 = O
XXV
As regards the definition of Ar, see process A.1);
Rg, Rh independently of one another are C1-C4-alkyl radicals (XXIIIa = XXIII where Rg = H and Rh = CH3; XXIVa = XXIV
where Rg = H und Rh = CH3).
As regards the procedure of the nucleophilic substitution reaction XXa + XXIII, reference may be made to the informa-tion given in Section A.13).
The subseguent cleavage of the reaction product XXIV i8 carried out with a halogen, preferably with chlorine or bromine, at between the melting point and the boiling point of the reaction mixture, preferably at 0-100~C.
As a rule, the reaction is carried out in an inert organic solvent, e.g. a hydrocarbon such as n-~ ne, a halogenated hydrocarbon such as dichloromethane or an ether such as tetrahydrofuran.
Finally, the halomethyl ether XXV is subjected to an Arbuzov reaction with a trialkyl phosphite XII. As regards the procedure of this reaction, reference may be made to the information given in Section A.12).
A.15) by reacting an aldehyde VIa with a trichloromethanephos-phonic acid derivative XXVI in the presence of an alkyl-lithium compound XXVII:

_ 0050/46587 CA 0224~4l l998-08-06 y (C1-C4-alkyl)-Li Ar--CHO +C13C--~ Z2R2 ~ I ~ X = -CH=C(Cl)-~
XXVII
5 VIa XXVI

As regards the definition of Ar, see process A.1).
Normally, -the phosphonic acid derivative XXVI is first reacted with the alkyllithium compound XXVII at between the melting point and the boiling point of the reaction mix-ture, preferably at from (-80) to (-50)~C. Normally, the reaction is carried out in an inert organic solvent/
diluent, e.g. a hydrocarbon such as n-hexane or an ether such as tetrahydrofuran.
The reaction product is reacted with the aldehyde VIa, pre-ferably without working up, during which process the reac-tion temperature is preferably raised to approximately 20~C.
A.16) by diazotizating of pyridylanilines II, reacting the resulting diazonium salts with phosphorus trichloride and reacting the reaction products with nucleophiles H-OR1 or H-OR2 {see, for example, E. Klumpp, G. Eifert, P. Born, J. Szulagyi, Chem. Ber. 122, (1989), 2021; G.O. Doak et al., J. Am. Chem. Soc. 75, (1953), p. 683, 1379, 4903 and 4905}:

ArNH2 1) diazotization I ~ X = bond; y, z1, z2 = O
II 2) PCl 3) H-ORl/H-OR2 As regards the diazotization, reference may be made to the information given in section A.1).
The diazonium salt is preferably isolated prior to the reaction using phosphorus trichloride, for example as the halide, tetrafluoroborate or hexafluorophosphate. The reac-tion itself is generally carried out in an inert organic solvent, e.g. a hydrocarbon such as n-hexane and toluene, a halogenated hydrocarbon such as dichloromethane, an ether such as tetrahydrofuran, or an aprotic solvent such as ace-tonitrile, dimethylformamide and dimethyl sulfoxide.

0050/46587 CA 0224~54l l998-08-06 In general, the process is carried out between the melting point and the boiling point of the reaction mixture, pre-ferably at from 0 to 100~C.
The subseguent conversion into I is preferably carried out using water as the nucleophile.
A.17) by reacting an aryl halide/triflate of the formula IV with a dialkyl phosphite XIII in the presence of a base and of a transition metal catalyst {see, for example, A. Ca~telnuovo, J. Calabrese, J. Am. Chem. Soc. 11~ (1990), 4324 ; T. Hirao et al., Bull. Chem. Soc. Jpn. 55 (1982), 909}:

I base Ar- Br + Hpo[o(cl-c4-alkyl)~2 O-SO2CF3 cat.
IV XIII
ao I ~ X = bond y, zl, z2 = o Examples of suitable bases are amines such as triethyla-mine.
A suitable catalyst is preferably a palladium compound, for example tetrakis(triphenylphosphine)palladium. Apart from this, reference may be made to the information given in section A. 2) .
B) Derivatization of substituted 2-phenylpyridines of the for-mula I:
B.l) Hydrogenation of substituted 2-phenylpyridines I where X is 1,2-ethenediyl or a halogen-substituted methylene, 1,2-ethanediyl or 1,3-propanediyl bridge (cf., for example, C.N. Robinson, P.K. Li. J.F. Addison, J. Org. Chem. 37 (1972) 2939; G.T. Lowen, M.R. Almond, J. Org. Chem. 59 (1994) 4548}:

0050/46587 CA 0224~41 1998-08-06 I~X =~ubst. or unsubst. I~x=subst. or 1,2-ethenediyl, or chlorine-, unsubst.
bromine- or iodine-substituted methylene, methylene, 1,2-ethanediyl or ~ 1,2-ethanediyl o~
1,3-propanediyl bridge, which, 1,3-propanediyl if desired, can have attached to it further substitutents~

As regards the definition of Ar, see process A.1).
~he hydrogenation is carried out either with hydrogen in the presence of a catalyst conventionally used for this 15 purpose, such as palladium or platinum on active charcoal or Raney nickel, at from 0 to 150~C and a hydrogen pressure of approx. 1 to 200 bar, or with a metal hydride such as sodium borohydride and lithium aluminum hydride at from 0~C
to the boiling point of the reaction mixture.
ao Examples of solvents which are suitable ~or the hydrogena-tion with hydrogen are water, the lower alcohols such as methanol and ethanol, ethers such as diethyl ether and tetrahydrofuran or esters such as ethyl acetate.
When reacting the starting compound with a metal hydride, the process i8 preferably carried out in an inert organic solvent, in particular an ether such as diethyl ether and tetrahydrofuran.
B.2) Hydrolysis of substituted 2-phenylpyridines I, conversion of the process products into phosphonyl halides, and reac-tion of the latter with nucleophiles:

- ; -0050/46587 CA 0224~41 l998-08-06 O o O
Ar- X- P--0R21ysis~ Ar-X - P~-OH- ~ Ar- X - !C~ Y=O~
ORl OH Cl I ~y,zl z2=o~I ~Y,zl~z2=o;Rl~R2=H~ XXVIIIa hydrolysi~

1~1 Ar--X-- p--oR2 ~ Y,Z2=O~
OH Cl 15 I~Y~Zl Z2=o: Rl=H~ XXIXa Ar- X- ~--cl~-XXIVa-~ ~Ar-X - p--oR2 ~ Ar-X -. oR2 Cl OH Cl XXVIIIbI ~ Y=S;z1, Z2=o; R1=H~ XXIXb I~Y=S ~ I ~Y=S;Z2=

As regards the definition of Ar, see process A.1).
In this process, the substituted 2-phenylpyridines I are first cleaved hydrolytically (acidic or alkaline) or, if 35 and/or R2 is a benzyl or allyl radical, also hydrogenolyti-cally, to give phosphonic acids and phosphonic monoesters I. If desired, the cleavage can also be carried out by means of a reaction with a tri(C1-C4-alkyl)silyl halide such as chlorotrimethylsilane, iodotrimethylsilane or a 40 mixture of chlorotrimethylsilane and alkali metal iodine.
The cleavage products can then be converted into the corre-sponding phosphonyl monochlorides or phosphonyl dichlorides XXVIIIa and XXIXa by reaction with a halogenating agent 45 such as oxalyl chloride, thionyl chloride and phosphorus pentachloride.

0050/46587 CA 0224~54l l998-08-06 If desired, the phosphonyl dichlorides XXVIIIa can be thio-nated in a manner known per se using a thionating agent such as phosphorus(V) sulfide and 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-dithione ( n Lawesson Reagent~) to give thionophosphonyl dichlorides ~vlllb. As regards useful solvents, temperature and ratios, reference may be made to the information given in DE-A 19 504 188 under process D).
Finally, further substituted 2-phenylpyridines I are acces-sible by reacting XXVIII and XXIX with nucleophiles HZlR
or Hz2R2 The chlorophosphonates XXIXa can be converted into the thionophosphonic monoesters XXIXb for example by conversion with sodium hydrogen sulfide.
As regards the procedure of the reaction and the ratios of the reactants, reference may be made, for example, to ao Houben-Weyl, Methoden der Organischen Chemie ~Methods in Organic Chemi~try], Georg Thieme Verlag, Stuttgart, Vol.
12/1, 4th Edition 1963, pp. 387 et seq., 407 et seq. and 557 et seg.; Vol. E2 1982, pp. 300 et seq. and 419 et seq.
25 B.3) Elimination of hydrogen halide from compounds I where X = -CH2-CH(halogen)- or -CH=C(halogen)-:
I {X = -CH2-CH(halogen) } base~ I {X= -CH=CH-}

I IX = -CH=C(halogen)-} base I {X = -C_C-}

The process is normally carried out in water or in an inert organic solvent, e.g. an alcohol such as ethanol, an ether such as diethyl ether, tetrahydrofuran and dioxane, or an aprotic solvent such as acetonitrile, dimethylformamide and dimethyl sulfoxide.
Examples of suitable bases are alkali metal hydroxides, alkali metal carbonates, alkali metal hydrides, alkyl-lithium compounds such as butyllithium, or organic amines such as triethylamine, 1,4-diazabicyclo[2.2.2.]octane (DABCO) and 1,8-diazabicyclo[5.4Ø]undec-7-ene (DBU).
In general, the reaction is carried out at from (-100)~C to the boiling point of the reaction mixture, preferably at from 20 to 100~C.

r 0050/46587 CA 0224~4l l998-08-06 C) Oxidation of substituted phenylpyridines of the formula I
where n is zero and the substituent -X-P(=Y)(ZlR1)(Z2R2) does not contain sulfur, in a manner known per se {cf., for exam-ple, A. Albini & S. Pietra, heterocyclic N-oxides, CRC-Press Inc., Boco Raton, USA 1991; H.S. Mosher et al., Org. Synth.
Coll. Vol. IV 1963, page 828; E.C. Taylor et al., Org. Synth.
Coll. Vol. IV 1963, page 704; T.W. Bell et. al., Org. Synth.
~9 (1990), page 226}:
oxidation I(n=O) ~ I(n=1) Amongst the oxidants conventionally used for oxidizing the pyridine ring, reference may be made by way of example to peracetic acid, trifluoroperacetic acid, perbenzoic acid, m-chloroperbenzoic acid, monopermaleic acid, magnesium mono-perphthalate, sodium perborate, Oxone~ (contains peroxydisul-fate), pertungstic acid and hydrogen peroxide.
Examples of suitable solvents are water, sulfuric acid, car-boxylic acids such as acetic acid and trifluoroacetic acid, and halogenated hydrocarbons such as dichloromethane and chloroform.
Normally, the reaction mixture is successfully oxidize~ at from 0~C to boiling point.
The oxidant is normally employed in at least eguimolar amounts based on the starting compound. In general, an OE cess of oxidant has proved to be especially advantageous.
Unless otherwise specified, all processes described hereinabove are expediently carried out under atmospheric pressure or under 35 the inherent pressure of the reaction mixture in ~uestion. The reactants are generally employed in a molar ratio of from 0.95:1 to 5:1.
In general, the reaction mixtures are worked up by methods known 40 per se, for example by diluting the reaction solution with water ~ollowed by isolation of the product by means of filtration, crystallization or solvent extraction, or by removing the solvent, partitioning the residue in a mixture of water and a suitable organic solvent and working up the organic 45 phase to give the product.
The substituted 2-phenylpyridines I can be obtained upon prepara-- - -~ -- --tion in the form of isomer mixtures which, however, if desired, can be separated into the pure isomers by the methods conven-tionally used for such cases, such as crystallization or chroma-tography, also on an optically active adsorbate. Pure optically 5 active isomers can be prepared advantageously from suitably optically active starting materials.
Agriculturally useful salts of the compounds I can be forme~ by reaction with a base of the correspsn~;ng cation, preferably an l0 alkali metal hydroxide or alkali metal hydride, or by reaction with an acid of the corresponding anion, preferably o~ hydrochlo-ric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
15 Salts of I whose metal ion is not an alkali metal ion can also be prepared in the customary manner by double decomposition of the corresponding alkali metal salt, also ~mmo~;um~ phosphonium, 5ul-fonium and sulfoxonium salts by means of ammonia, phosphonium hydroxide, sulfonium hydroxide or sul~oxonium hydroxide.
The compounds I and their agriculturally useful salts are suit-able as herbicides, both in the form of isomer mixtures and in the form of the pure isomers. The herbicidal compositions com-prising I effect very good control of vegetation on non-crop 25 areas, especially at high rates of application. In crops such as wheat, rice, maize, soybeans and cotton they act against broad-leaved weeds and grass weeds without damaging the crop plants substantially. This effect is observed especially at low rates of application.
Dep~n~;ng on the application method in ~uestion, the compounds I, or herbicidal compositions comprising them, can additionally be employed in a further number of crop plants for ~lim;nAting unde~
sirable plants. Examples of suitable crops are the ~ollowing:
35 Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus offi-cinalis, seta vulgaris spec. altissima, Beta vulgaris spec. rapa, Brassica napus var. napus, srassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carth~ml~,c tinc-torius, Carya illinoinensis, Citrus limon, Citrus sinensis, Cof-40 fea arabica (Coffea canephora, Coffea liberica), Cucumis sativus,Cynodon dactylon, Daucus carota, Elaeis guineensis, Fragaria ves-ca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossy-pium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoea batatas, 45 Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec., Nicotiana tabacum (N.rustica), Olea europaea, Oryza 0050/46587 CA 02245541 l998-08-06 sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus spec., Pisum sativum, Prunus avium, Prunus persica, Pyrus commu-nis, Ribes sylvestre, Ricinus c~m~lln;s, Saccharum officinarum, Secale cereale, Solanum tuberosum, Sorghum bicolor (s. vulgare), 5 Theobroma cacao, Trifolium pratense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera and Zea mays.
Moreover, the compounds I can also be used in crops which toler-ate the action of herbicides due to br~e~;ng including genetic 10 engineering methods.
Furth~rmore, the substituted 2-phenylpyridines I are also suit-able for the desiccation and/or defoliation of plants.
15 As desiccants, they are especially suitable for aesiccating the aerial parts of crop plants such as potatoes, oilseed rape, sun-flowers and soybeans. This allows completely mec~n;cal harvest-ing of these important crop plants.
20 Also of economic interest is facilitated harvesting, which is made possible by concentrating, over a period of time, dehis-cence, or reduced adhesion to the tree, in the case of citrus fruit, olives or other species and varieties of pomaceous fruit, stone fruit and nuts. The same me~n;sm, i.e. promotion of the 25 formation of abscission tissue between fruit or leaf and shoot of the plants is also essential for readily controllable defoliation of useful plants, in particular cotton.
Moreover, a shortened period of time within which the individual 30 cotton plants ripen results in an increased fiber ~uality after harvesting.
The compounds I, or the compositions comprising them, can be employed, for example, in the form of directly sprayable agueous 35 solutions, powders, suspensions, also highly-concentrated a~ueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, materials for spreading or granules, by means of spraying, atomizing, dusting, spre~;ng or pouring.
The use forms depend on the intended purposes; in any case, they 40 should guarantee the finest possible distribution of the active ingredients according to the invention.
Suitable inert auxiliaries are essentially: mineral oil fractions of medium to high boiling point such as kerosene and diesel oil, 45 furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. paraffins, tetrahydronaphthalene, alkylated naphthalenes and their deriva-_ -OOSO/46587 CA 0224~s4l 1998-08-06 tives, alkylated benzenes and their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cycloh~x~none~ strongly polar solvents, e.g. amines such as N-methylpyrrolidone and water.
s Agueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible gran-ules by adding water. To prepare emulsions, pastes or oil disper-sions, the substances, as such or dissolved in an oil or solvent, lO can be homogenized in water by means of wetting agent, tackifier, dispersant or emulsi~ier. However, it is also possible to prepare concentrates composed of active substance, wetting agent, tackif-ier, dispersant or emulsifier and, if appropriate, solvent or oil, and these concentrates are suitable for dilution with water.

Suitable surfactants are the alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, e.g. ligno-, phe-nol-, naphthalene- and dibutylnaphthalenesulfonic acid, and of fatty acids, of alk~l- and alkylaryl sulfonates, of alkyl sul-20 ~ates, lauryl ether s~l~ates and fatty alcohol sulfates, andsalts of sulfated hexa-, hepta- and octadecanols, and of fatty alcohol glycol ether, condensates o~ sul~onate~ naphthalene and its derivatives with ~ormaldehyde, con~n~ates of naphthalene, or of the naphthalenesulfonic acids, with phenol and formaldehyde, 25 polyoxyethylene octylphenyl ether, ethoxylated isooctyl-, octyl-or nonylphenol, alkylphenyl and tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol/

ethylene oxide condensates, ethoxylated castor oil, polyoxyethy-lene alkyl ethers or polyoxypropylene alkyl ethers, lauryl alco-30 hol polyglycol ether acetate, sorbitol esters, lignin-sulfite with li~uors or methylcellulose.

Powders, materials for spreading and dusts can be prepared by m;x;ng or concommitantly grinding the active substances with a 35 solid carrier.

Granules, e.g. coated granules, impregnated granules and homoge-neous granules, can be prepared by binding the active ingredients to solid carriers. Solid carriers are mineral earths such as sil-40 icas, silica gels, silicates, talc, kaolin, limestone, lime,chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic material, fertilizers such as ~mmon~um sulfate, ~mm~n;um phos-phate, Ammo-n;u-m~ nitrate, ureas and products of vegetable origin 45 such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders or other solid carriers.

_ 0050/46587 CA 0224~4l l998-08-06 The concentrations of the active ingredients I in the ready-to-use products can be varied within wide ranges. In general, the formulations comprise approximately from 0.001 to 98% by weight, preferably 0.01 to 95% by weight, of at least one active ingredi-5 ent. The active ingredients are employed in a purity of from 90%
to 100%, preferably 95% to 100% (according to NMR spectrum).
The formulation examples below illustrate the preparation of such products:
. 20 parts by weiqht of the compound No. Iaa.3 are dissolved in a mixture composed of 80 parts by weight of alkylated benzene, 10 parts by weight of the adduct of 8 to 10 mol of ethylene oxide and 1 mol of oleic acid N-monoethanolamide, 5 parts by weight of calcium dodecylbenzenesulfonate and 5 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an agueous dispersion which comprises 0.02% by weight of the active ingredient.
II. 20 parts by weight of the compound No. Ica.3 are dissol~ed in a mixture composed of 40 parts by weight of cyclohexa-none, 30 parts by weight o$ isobutanol, 20 parts by weight of the adduct of 7 mol of ethylene oxide and 1 mol of iso-octylphenol and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an agueous dispersion which comprises 0.02% by weight of the active ingredient.
III. 20 parts by weight of the active ingredients No. Ida.2 are dissolved in a mixture composed of 25 parts by weight of cycloh~none, 65 parts by weight of a mineral oil fraction of boiling point 210 to 280~C and 10 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil.
Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous disper-sion which comprises 0.02% by weight of the active ingredi-ent.
IV. 20 parts by weight of the active ingredient No. Ifa.3 are mixed thoroughly with 3 parts by weight of sodium diisobu-tylnaphthalene-a-sulfonate, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of pulverulent silica gel and the mixture is ground in a ~er mill. Finely distributing 0050/46587 CA 0224ss4l l998-08-06 the mixture in 20,000 parts by weight of water gives a spray mixture which comprises 0.1% by weight of the active ingredient.
5 V. 3 parts by weight of the active ingredient No. Icy.2 are mixed with 97 parts by weight of finely divided kaolin.
This gives a dust which comprises 3% by weight of the active ingredient.
10 VI. 20 parts by weight of the active ingredient No. Icy.3 are mixed intimately with 2 parts by weight of calcium dodecyl-benzenesulfonate, 8 parts by eight of fatty alcohol poly-glycol ether, 2 parts by weight of the sodium salt of a phenol/urea/formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. This gives a stable oily dis-persion.
VII. 1 part by weight of the compound No. Ina.3 is dissolved in a mixture composed of 70 parts by weight of cycloh~none, ao 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. The mixture can subseguently be diluted with water to give the desired con-centration of active ingredient. This gives a stable emulsion concentrate.
VIII. 1 part by weight of the compound No. Iia.38 is dissolved in a mixture composed o~ 80 parts by weight of cyclohexanone and 20 parts by weight of Wettol~ EM 31 (= non-ionic emul-sifier based on ethoxylated castor oil). The mixture can subseguently be diluted with water to give the desired con-centration of active ingredient. This gives a stable emulsion concentrate.
The active ingredients I, or the herbicidal compositions compris-35 ing them, can be applied pre- or post-emergence. If the active ingredients are less well tolerated byScertain crop plants, application techni~ues may be used in which the herbicidal com-positions are sprayed, with the aid of the spray apparatus, in such a way that they come into as little contact, if any, with 40 the leaves of the sensitive crop plants while reaching the leaves of undesirable plants which grow underneath, or the bare soil (post-directed, lay-by).
Depending on the intended aim of the control measures, the 45 season, the target plants and the growth stage, the application rates of active ingredient I are from 0.001 to 3.0, preferably 0.01 to 1.0 kg/ha active substance (a.s.).

0050/46587 CA 0224~41 l998-08-06 To widen the spectrum of action and to achieve synergistic effect~, the substituted 2-phenylpyridines I can be mixed and applied jointly with a large number of representatives of other 5 groups of herbicidally or growth-regulatory active ingredients.
Suitable components in mixtures are, for example, 1,2,4-thiadia-zoles, 1,3,4-thiadiazoles, amide~, aminophosphoric acid and its derivatives, aminotriazoles, anilides, aryloxy-/hetaryloxyAl k~n; c acids and their derivatives, benzoic acid and its derivatives, 10 benzothiadiazinones, 2-(hetaroyl/aroyl)-1,3-cyclohexanediones, hetaryl aryl ketones, benzylisoxazolidinones, meta-CF3-phenylderi-vatives, carbamates, guinolinecarboxylic acid and its deriva-tives, chloroacetanilides, cyclohexane-1,3-dione derivatives, diazines, dichloropropionic acid and its derivatives, dihydroben-15 zofuranes, dihydrofuran-3-ones, dinitroanilines, dinitrophenoles, diphenyl ethers, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrophthalimides, oxadiazoles, oxiranes, phenols, aryloxy- and hetaryloxyphenoxypropionic esters, 20 phenylacetic acid and its derivatives, 2-phenylpropionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazines, pyridi-necarboxylic acid and its derivatives, pyrimidyl ethers, sulfona-mides, sulfonylureas, triazines, triazinones, triazolinones, triazole carboxamides and uracils.
as Moreover, it may be advantageous to apply the compounds I, alone or in combination with other herbicides, in the form o~ a mixture with additional other crop protection agents, for example with pesticides or agents for controlling phytopathogenic fungi or 30 bacteria.'Also of interest is the miscibility with mineral salt solutions which are employed for treating nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.
35 Preparation examples Example 1 Diethyl 1-chloro-2-(2-chloro-5-(3-chloro-5-trifluoromethylpy-rid-2-yl)-4-fluorophenyl)ethylphosphonate (No. Icy.3) 3 g (9 mmol) of 2-chloro-5-(3-chloro-5-trifluoromethyl-pyrid-2-yl)-4-fluoroaniline were added to a solution of 30.3 g (0.19 mol) of diethyl vinylphosphonate, 1.4 g of copper(II) chlo-ride (10 mmol) and 1 g (10 mmol) of tert-butyl nitrite in 150 ml 45 of acetonitrile. After 3 hours, 200 ml of methyl tert-butyl ether were added to the reaction mixture. The organic phase was subse-quently washed twice with water, then dried over magnesium sul-0050/46587 CA 0224~4l l998-08-06 fate and finally concentrated. ~he crude product was purified by column chromatography (eluent: hexane/ethyl acetate = 4:1).
Yield: 1.6 g.
5 Example 2 Diethyl 1-chloro-2-(2-chloro-5-(3-chloro-5-trifluoromethyl-pyrid-2-yl)-4-fluorophenyl)vinylphosphonate (No. Iiy.3) 3 ml of a butyllithium solution (1.5 M in hexane; 4.5 mmol) were 10 added to a solution, cooled to (-70)~C, of 2.3 g (9 mmol) of die-thyl trichloromethanephosphonate in 30 ml of tetrahydrofuran in such a way that the temperature did not rise above (-6S)~C. Stir-ring of the mixture was then continued for 1 hour at (-65) to (-70)~C, whereupon a solution of 1 g (3 mmol) of 2-chloro-15 5-(3-chloro-5-trifluoromethylpyrid-2-yl)-4-fluorobenzaldehyde in 20 ml of tetrahydrofuran was slowly added dropwise. After the mixture had been stirred for a further 30 minutes, the cooling bath was removed and the mixture was allowed to come to room tem-perature. The reaction solution was subsequently washed with sat-20 urated aqueous sodium chloride solution, then dried over magne-sium sulfate and finally concentrated. The crude product was p~-rified by column chromatography on silica gel (eluent: hexane/
ethyl acetate = 4:1). Yield: 0.8 g.
25 Example 3 Dimethyl 1-bromo-2-t2-chloro-5-(3-chloro-5-trifluoromethyl-pyrid-2-yl)phenyl]ethylphosphonate (No. Ida.~) By following a method similar to the one described for Example 1 30 and using 32.6 g (0.24 mol) of dimethyl vinylphosphonate, 3.13 g (14 mmol) of copper(II) bromide, 1.33 g (13 mmol) of tert-butyl nitrite and 3.6 g (12 mmol) of 2-chloro-5-(3-chloro-5-trifluoro-methylpyrid-2-yl)aniline, 1.2 g of the desired product of value were obtained.
Example 4 Diethyl 2-chloro-5-(3-chloro-5-trifluoromethylpyrid-2-yl)ben-zyloxymethylphosphonate (No. Ina.3) 40 To a solution of 0.66 g (3.9 mmol) of diethyl hydroxymethylphos-phonate in 30 ml of tetrahy~rofuran there were added 0.1 g (3.6 mmol) of sodium hydride and, after the mixture had been stirred for 15 minutes, 1 g (2.6 mmol) of 2-chloro-5-(3-chlo-ro-5-trifluoromethylpyrid-2-yl)benzyl bromide. The mixture was 45 subseguently stirred for 16 hours. The reaction mixture was then concentrated. The crude product obtained was purified by means of silica gel chromatography (eluent: hexane/ethyl acetate = 1:1).

0050/46587 CA 0224~4l l998-08-06 Yield: 0.8 g.
Example 5 Diethyl 2-chloro-5-(3-chloro-5-trifluoromethylpyrid-2-yl)-4-fluo-5 rophenoxymethylphosphonate (No. Ioy.3) 0.14 g (0.78 mmol) of bromine was added to a solution of 0.3 g (0.78 mmol) of 3-chloro-2-[4-chloro-2-fluoro-5-(methylthiome-thoxy)phenyl]-5-trifluoromethylpyridine in lO ml of tetrachloro-10 methane. After the mixture had been stirred for 2 hours, it wasconcentrated. The residue was treated with 20 ml of triethyl phosphite. Stirring was subse~uently continued for 16 hours, whereupon excess phosphite was removed under a high vacuum.
Yield: 0.2 g.
Precursor 5.1 3-Chloro-2-[4-chloro-2-fluoro-5-(methylthiomethoxy)phenyl]-5-tri-fluoromethylpyridine 20 0.1 g (4.4 mmol) o~ sodium hydride was added to a solution of 1.3 g (4 mmol) of 2-chloro-5-(3-chloro-5-tri~luoromethyl-pyrid-2-yl)-4-fluorophenol in 50 ml o~ dimethylformamide. After the mixture has been stirred for 1 hour, it was treated with 0.5 g (5.2 mmol) of methylthiomethyl chloride. Then, the mixture 25 was stirred for another hour. For working-up, the reaction mix-ture was treated with 50 ml of water. The product was then ex-tracted with 100 ml of methyl tert-butyl ether. The organic phase was dried over magne~ium sulfate and finally concentrated.
Yield: 0.3 g.
30 lH NMR (270 MXz; in CDCl3): ~ [ppm] = 2.31 (5, 3H), 5.24 (s, 2H), 7.12 (d, lH), 7.30 (d, lH), 8.08 (s, lH), 8.88 (5, lH).
Example 6 Diethyl 2-chloro-5-(3-chloro-5-trifluoromethylpyrid-2-yl)benzyl-35 phosphonate (No. Iaa.3) A solution of 1 g (2.6 mmol) of 2-chloro-5-(3-chloro-5-trifluoro-methylpyrid-2-yl)benzyl bromide in 10 ml of triethyl phosphite was heated for 12 hours at 80 to 90~C, whereupon excess triethyl 40 phosphite was distilled off under a high vacuum. Yield: 1.1 g.
Example 7 1-Chloro-2-[2-chloro-5-(3-chloro-5-trifluoromethyl-pyrid-2-yl)-4-fluorophenyl]ethylphosphonic acid (No. Icy.1) 0.7 g (4.2 mmol) o~ potassium iodide and 0.46 g (4.2 mmol) of chlorotrimethylqilane were added to a solution o~ 0.7 g (1.4 mol) 0050/46587 CA 0224~41 1998-08-06 of diethyl 1-chloro-2-[2-chloro-5-(3-chloro-5-trifluoromethylpy-rid-2-yl)-4-fluorophenyl]ethylphosphonate in 20 ml of acetoni-trile. The mixture was then heated for 4 hours at 50 to 60~C, whereupon it was concentrated. 20 ml of water and 50 ml of ethyl 5 acetate were added to the residue. The organic phase was separated off, dried over magnesium sulfate and finally con~n-trated. Yield: quantitative.
Example 8 10 Diethyl 1-cyano-2-[2-chloro-5-(3-chloro-5-trifluoromethyl-pyrid-2-yl)phenyl~ethylphosphonate (No. If a . 3) 2.27 ml (3.6 mmol) of a 1.6 M butyllithium solution in n-hexane were added to a solution, cooled to (-78)~C, of 0.69 g (3.89 mmol) 15 of diethyl cyanomethylphosphonate in 50 ml of tetrahydrofuran.
After the mixture had been stirred for 1 hour, it was treated with 1 g (2.6 mmol) of 2-chloro-5-(3-chloro-5-tri~luoromethylpy-rid-2-yl)benzyl bromide, dissolved in 10 ml of tetrahydrofuran.
The mixture was then stirred for another 16 hours at approximate-ao ly 20~C. It was then concentrated, and the residue which r~mA;neAwas treated with 50 ml of ethyl acetate. The product-containing organic phase was separated off, washed with water and saturated a~ueous sodium chloride solution, dried over magnesium sulfate and finally concentrated. The crude product was purified by means 25 of silica gel chromatography (eluent: hexane/ethyl acetate =
4:1). Yield: 0.6 g.
Example 9 Diethyl 1-chloro-2-[2-chloro-5-(3-chloro-5-trifluoromethyl-30 pyrid-2-yl)phenyl~vinylphosphonate (No. Iia.3) By following a method similar to Example 2 and using 33.7 g (0.13 mol) o~ diethyl trichloromethanephosphonate, 41 ml of a butyllithium solution (1.6 M in n-hexane; 63 mmol n-butyllithium~
35 and 8.3 g (26 mmol) of 2-chloro-5-(3-chloro-5-trifluoromethyl-pyrid- 2-yl)-benzaldehyde, 10 g of the desired product of value were obtained.
Example 10 40 1-Chloro-2-t2-chloro-5-(3-chloro-5-trifluoromethylpyrid-2-yl)-phenyl]vinylphosphonic acid (No. Iia.1) By following a method similar to the one described for Example 7 and usinq 4 g (8.1 mmol) of diethyl 1-chloro-2-[2-chloro-45 5-(3-chloro-5-trifluoromethylpyrid-2-yl)phenyl]vinylphosphonate, 4 g (24 mmol) of potassium iodide and 2.7 g (24 mmol) of chloro-trimethylsilane, 3 g of the desired product of value were -0050/46587 CA 0224554l l998-08-06 obt~; n~ .
Example 11 Diallyl 1-chloro-2-[2-chloro-5-(3-chloro-5-trifluoromethyl-5 pyrid-2-yl)phenyl~vinylphosphonate (No. Iia.32) 0.9 g (7 mmol) of oxalyl chloride was added to a solution of 1 g (2.3 mmol) of 1-chloro-2-[2-chloro-5-(3-chloro-5-trifluoromethyl-pyrid-2-yl)phenyl]vinylphosphonic acid in 15 ml of 1,2-dichloro-10 ethane. Then, the reaction mixture was heated briefly to refluxtemperature and subse~uently concentrated. The resulting acid chloride was dissolved in 50 ml of dichloromethane. After 0.55 g (6.3 mmol) of pyridine and 0.4 g (6.3 mmol) of allyl alcohol had been added, the mixture was stirred ~or a further 16 hours. The 15 mixture was then treated with water. The organic phase was subse-~uently separated off, dried over magnesium sul~ate and concen-trated. The crude product was purified by means of silica gel chromatography (eluent: hexane/ethyl acetate = 4:1). Yield:
0.2 g.
In addition to those described above, a further number of substi-tuted 2-phenylpyridines which were, or can be, prepared by simi-lar methods are listed in Table 2 below:

0050/46587 CA 0224~41 1998-08-06 Table 2 F C ~1l ll I {R3, R5 = Cl; R6 = CF3; n = O }
zlRl No. R4 -X- -p(=y)(zlRl(z2R2) M.p./lH N~
(~ in [ppm]), MS [m/z]
Iaa.3 H -CH2- p(=o)(OC2Hsk 1.27 (t, 6H), 3.44 (d, 2H), 4.09 (quint., 4H), 7.51 (d, lH), 7.64 (dd, lH), 7.88 (d, lH), 8.03 (d, lH), 8.83 (d, lH) Ica.2 H -CH2-CH(Cl)- p(=O)(OCH3)2 426 [M-Cl]~
Ica.3 H -CH2-CH(Cl)- p(=o)(oc2Hs)2 454 [M-Cl]+
Ida.2 H -CH2-CH(Br)- -P(=O)(OCH3)2 504 [M-H]+, 470 [M-Cl]+
Ida.3 H -CH2-CH(Br)- P(=O)(OC2Hs)2 1.38 (t, 6H), 3.22 (ddd, lH), 3.82 (ddd, lH), 4.27 (m,5H), 7.52 (d, lH), 7.68 (dd, lH), as 7.75 (d, lH), 8.08 (s, lH), 8.86 (s, lH) Ifa.3 H -CH2-CH(CN)- -P(=O)(Oc2Hs)2 1.39 (t, 3H), 1.43 (t, 3H), 3.18 (ddd, lH), 3.42 (ddd, lH), 3 0 3.56 (ddd, lH), 4.30 (m, 4H), 7.54 (d, lH), 7.73 (dd, lH), 7.83 (d, lH), 8.05 (d, lH), 8.85 (d, lH) Icy.l F -CH2-CH(CI)- p(=o)(oH)2 3.12 (ddd, lH), 3.59 (brd, lH), 4.19 (brt, lH), 7.64 (d, lH), 7.68 (d, lH), 8.66 (s, lH), 9.10 (s, lH), 10.95 (s, 2H) Icy.2 F -CH2-CH(Cl)- P(=O)(OCH3)2 3.14 (ddd, lH), 3.67 (ddd, lH), 3.88 (d, 3H), 3.94 (d, 3H), 4.26 (dt, lH), 7.29 (d, lH), 7.45 (d, lH), 8.07 (s, lH), 8.86 (s, lH) Icy.3 F -CH2-CH(Cl)- P(=~)(~C2Hs)2 1.39 (t, 3H), 1.40 (t, 3H), 3.12 (dt, lH), 3.70 (ddd, lH), 4.20-4.33 (m, 5H), 7.29 (d, lH), 7.46 (d, lH), 8.08 (s, lH), 8.88 (s, lH) 0~50/46587 CA 0224~41 1998-08-06 No. R4 -X- -P(---Y)(zlRl(z2R2) M.p./lH NMR
(~ in [ppm]), MS [m/z]
Ina.3 H -CH2-OCH2- P(=~)(~C2Hs)2 1.32 (t, 6H), 3.90 (d, 2H), 4.19 (quint., 4H), 4.83 (s, 2H), 7.50 (d, lH), 7.68 (dd, lH), 7.92 (d, lH), 8.07 (s, lH), 8.84 (s, lH) Iia. l H -CH=C(CI)- _p(=o)(OH)2 resin Iia.3 H -CH=C(Cl)- p(=o)(oc2H5)2 1.42 (t, 6H), 4.24 (m, 4H), 7.58 (d, lH), 7.77 (dd, lH), 7.96 (d, lH), 8.07 (d, lH), 8.32 (d, lH), 8.86 (d, lH) Iia.32 H -CH=C(Cl)- P(=O)(OCH2-CH=CH2)2 4.67 (m, 4H), 5.29 (d, 2H), 5.43 (d, 2H), 5.98 (m, 2H), 7.58 (d, lH), 7.77 (dd, lH), 7.98 (d, lH), 8.06 (d, lH), 8.31 (d, lH), 8.86 d, lH) Iia.36 H -CH=C(Cl)- p(=o)(ocH2-c=cH)2 2.62 (t, 2H), 4.84 (dd, 4H), 7.59 (d, lH), 7.78 (dd, lH), 8.01 (d, lH), 8 06 (d, 1~, 8.33 (d, lH), 8.86 (d, lH) Iia.38 F -CH=C(Cl)- -P(=O)(OCH2-CO-OCH3)2 3.82 (s, 3H), 4.77 (dd, 2H), 4.86 (dd, 2H), 7.59 (d, lH), 7.78 (dd, lH), 8.06 (d, lH), 8.08 (d, lH), 8.36 (d, lH), 8.86 (d,lH) Iia.398 H -CH=C(Cl)- -P(=O)rN(CH3)- 1.92 (m, lH), 2.22 (m, lH), -CH2-CH2-CH2-N(CH3)] 2.72 (d, 6H), 3.16 (m, 2H), 3.39 (m, 2H), 7.56 (d, lH), 7.72 (dd, lH), 7.87 (d, lH), 8.06 (d, lH), 8.23 (d, lH), 8.86 (d, lH) 3 ~ Iiy.3 F -CH=C(Cl)- P(=~)(~C2Hs)2 1.41 (t, 6H), 4.154.30 (m, 4H), 7.36 (d, lH), 7.91 (d, lH), 8.09 (m, 2H), 8.89 (S, lH) Ioy.3 F -OCH2- P(=~)(~C2Hs)2 1.30 (m, 6H), 4.004.30 (m, 6H), 7.11 (d, lH), 7.15 (dd, lH), 8.06 (s, lH), 8.83 (s, lH) Use Examples (herbicidal activity) 40 The herbicidal action of the substituted 2-phenylpyridines I was ~mnn~trated by the following greenhouse experiments:

The culture containers used were plastic flowerpots cont~;n;ng loamy sand with approximately 3.0% of humus as substrate. The 45 seeds of the test plants were sown separately for each species.
For the pre-emergence treatment, the active ingredients, , 0050/46587 CA 0224~4l l998-08-06 -suspended or emulsified in water, were applied directly after sowing by means of finely distributing nozzles. The containers were irrigated gently to promote g~rm; n~ tion and growth and subseguently covered with translucent plastic hoods until the 5 plants had rooted. This cover caused uniform g~rm;n~tion of the test plants unless this was adversely affected by the active ingredients.
For the post-emergence treatment, the test plants were grown to a 10 plant height of from 3 to 15 cm, dep~n~;ng on the plant habit, and only then treated with the active ingredients which had been suspended or emulsified in water. To this end, the test plants were either sown directly and grown in the same containers, or they were first grown separately as seedlings and transplanted 15 into the test containers a few days prior to treatment. The rate of application for the post-emergence treatment was 15.6, 7.8, 3.9 or 1.9 g/ha a.s. ~active substance).
Dep~n~;ng on the species, the plants were kept at from 10 - 25~C
20 and 20 - 35~C, respectively. The test period extended over 2 to 4 weeks. During this time, the plants were tended, and their response to the individual treatments was evaluated.
Evaluation was carried out using a scale of from 0 to 100. 100 25 means no emergence of the plants, or complete destruction of at least the aerial parts, and 0 means no damage or normal course of growth.
The plants used in the greenhouse experiments belonged to the 30 ~ollowing species:

Scientific Name Common Name Amaranthus retroflexus redroot pigweed 35 Chenopodium album lambsquarters (goose foot) Galium aparine catchweed bedstraw Ipomoea subspecies morningglory Polygonum persicaria lady's thumb 40 Solanum nigrum black nightshade When rates of application of 3.9 and 1.9 g/ha a.s. were applied post-emergence, the compound No. Icy.3 was very effective against the abovementioned plants.

When rates of 15.6 and 7.8 g/ha a.s. were applied, the compound No. Icy.3 allowed a considerably better control of Amaranthus -, 0050/46587 CA 0224~4l l998-08-06 -retroflexus, Galium aparine, Ipomoea subspecies, Polygonum persi-caria and Solanum nigrum than the comparison compound A

5Cl Cl Cl ~

N ~ CH2 CH p - OC2Hs ~A), ~ N ~ N
10 F2HC OC2Hs which is known from ACS Symp. Ser. 584, (1995), 90.
15 Use Examples (desiccant/defoliant activity) The test plants used were young cotton plants with 4 leaves (without cotyledons) which had been grown under greenhouse conditions (relative atmospheric humidity 50 to 70%; day/night 20 temperature 27/20~C).
The young cotton plants were subjected to foliar treatment with aqueous preparations of the active ingredients (with an addition of 0.15% by weight of the fatty alcohol alkoxylate Plurafac~ LF
a5 7001), based on the spray mixture) until runoff point was reached.
The amount of water applied was 1000 l/ha (converted). After 13 days, the number of leaves shed and the degree of defoliation in % were determined.
30 No leaves were shed in the untreated control plants.

I) alow-fo~m,no~ionics r~ ofBASFAG

Claims (19)

We claim:

1. A substituted 2-phenylpyridine of the formula I

where the variables have the following meanings:
X is a chemical bond, 1,2-ethynediyl or - a methylene, 1,2-ethanediyl or 1,3-propylene bridge, which, if desired, can have attached to it a hydroxyl, amino or C1-C4-alkylamino substituent;
- methyleneoxymethylene, methylenethiamethylene, ethene-1,2-diyl or - oxymethylene, thiamethylene, oxyethylene or thiaethylene, bonded to the phenyl ring via the hetero atom, it being possible, if desired, for the last two chains to have a hydroxyl, amino or C1-C4-alkylamino attached to the carbon atom adjacent to the phosphorous;
and it being possible for each of the last-mentioned 10 bridges to have attached to it one or two of the following substituents: cyano, carboxyl, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, (C1-C4-alkoxy)carbonyl and/or di-(C1-C4-alkyl)amino;
Y is oxygen or sulfur;
Z1 is oxygen, sulfur or -N(R7)-;
Z2 is oxygen, sulfur or -N(R8)-;
R1, R2, R7 and R8 independently of one another are hydrogen, C1-C6-alkyl, C1-C6-haloalkyl, hydroxy-C1-C4-alkyl, cyano-C1-C4-alkyl, C1-C4-alkoxy-C1-C4-alkyl, C1-C4-haloalkoxy-C1-C4-alkyl, C3-C4-alkenyloxy-C1-C4-alkyl, C3-C4-alkynyloxy-C1-C4-alkyl, C3-C8-cycloalkoxy-C1-C4-alkyl, amino-C1-C4-alkyl, C1-C4-alkylamino-C1-C4-alkyl, di(C1-C4-alkyl)amino-C1-C4-alkyl, C1-C4-alkylthio-C1-C4-alkyl, C1-C4-haloalkylthio-C1-C4-alkyl, C3-C8-alkenylthio-C1-C4-alkyl, C3-C4-alkynylthio-C1-C4-alkyl, C1-C4-alkylsulfinyl-C1-C4-alkyl, C1-C4-haloalkylsulfinyl-C1-C4-alkyl, C3-C4-alkenyl-sulfinyl-C1-C4-alkyl, C3-C4-alkynylsulfinyl-C1-C4-alkyl, C1-C4-alkylsulfonyl-C1-C4-alkyl, C1-C4-haloalkylsulfonyl-C1-C4-alkyl, C3-C4-alkenylsulfonyl-C1-C4-alkyl, C3-C4-alkynylsulfonyl-C1-C4-alkyl, C3-C6-alkenyl, C3-C6-haloalkenyl, cyano-C3-C6-alkenyl, C3-C6-alkynyl, C3-C6-haloalkynyl, cyano-C3-C6-alkynyl, hydroxycarbonyl-C1-C4-alkyl, (C1-C4-alkoxy)carbonyl-C1-C4-alkyl, (C1-C4-alkylthio)carbonyl-C1-C4-alkyl, aminocarbonyl-C1-C4-alkyl, (C1-C4-alkyl)amino-carbonyl-C1-C4-alkyl, di(C1-C4-alkyl)amino-carbonyl-C1-C4-alkyl, C3-C8-cycloalkyl, C3-C8-cycloalkyl-C1-C4-alkyl, phenyl, phenyl-C1-C4-alkyl or 3- to 7-membered heterocyclyl or heterocyclyl-C1-C4-alkyl, it being possible, if desired, for all heterocycles to contain a carbonyl or thiocarbonyl ring member, and it being possible for all cycloalkyl, phenyl and heterocyclyl rings to be unsubstituted or to have attached to them one to four substituents, in each case selected from the group consisting of halogen, cyano, nitro, amino, hydroxyl, carboxyl, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfonyl, C1-C4-haloalkylsulfonyl, (C1-C4-alkyl)carbonyl, (C1-C4-haloalkyl)carbonyl, (C1-C4-alkoxy)carbonyl, (C1-C4-alkyl)carbonyloxy, (C1-C4-haloalkyl)carbonyloxy and di(C1-C4-alkyl)amino, or R1 and R2 or R1 and R7 and/or R2 and R8 in each case together form a 1,2-ethanediyl, 1,3-propylene, tetramethylene, pentamethylene or ethyleneoxyethylene chain which, if desired, can be substituted by one to four C1-C4-alkyl and/or one or two (C1-C4-alkoxy)carbonyl groups, or R1 and R2 together are 1,2-phenylene which can be unsubstituted or have attached to it one to three substituents, in each case selected from the group consisting of cyano, nitro, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy and C1-C4-haloalkoxy;

R3 is cyano, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy or C1-C4-haloalkoxy;
R4, R5 in each case are hydrogen or halogen;
R6 is halogen or C1-C4-haloalkyl;
n is zero or one;
or an agriculturally useful salt of a compound I.

2. The use of the substituted 2-phenylpyridines of the formula I
and of the agriculturally useful salts thereof, as claimed in claim 1, as herbicides or for the desiccation/defoliation of plants.

3. A herbicidal composition comprising a herbicidally active amount of at least one substituted 2-phenylpyridine of the formula I or of an agriculturally useful salt of I, as claimed in claim 1, and at least one inert liquid and/or solid carrier and, if desired, at least one surfactant.

4. A composition for the desiccation and/or defoliation of plants comprising such an amount of at least one substituted 2-phenylpyridine of the formula I or of an agriculturally useful salt of I, as claimed in claim 1, that it acts as a desiccant and/or defoliant, and at least one inert liquid and/or solid carrier and, if desired, at least one surfactant.

5. A process for the preparation of herbicidally active compositions, which comprises mixing a herbicidally active amount of at least one substituted 2-phenylpyridine of the formula I or of an agriculturally useful salt of I, as claimed in claim 1, and at least one liquid and/or solid carrier and, if desired, at least one surfactant.

6. A process for the preparation of compositions which act as desiccants and/or defoliants, which comprises mixing such an amount of at least one substituted 2-phenylpyridine of the formula I or of an agriculturally useful salt of I, as claimed in claim 1, that it acts as a desiccant/defoliant, and at least one liquid and/or solid carrier and, if desired, at least one surfactant.

7. A method of controlling undesirable vegetation, which comprises allowing a herbicidally active amount of at least one substituted 2-phenylpyridine of the formula I or of an agriculturally useful salt of I, as claimed in claim 1, to act on plants, their environment, or on seed.

8. A method for the desiccation and/or defoliation of plants, which comprises allowing such an amount of at least one substituted 2-phenylpyridine of the formula I or of an agriculturally useful salt of I, as claimed in claim 1, to act on plants that it acts as a desiccant/defoliant.

9. A method as claimed in claim 8, wherein cotton is treated.

10. A process for the preparation of substituted 2-phenylpyridines of the formula I where X is -CH2-CH(Cl)- or -CH2-CH(Br)-, which comprises diazotizing 3-pyridylanilines of the formula II

and reacting the resulting diazonium cations in the presence of a copper salt with vinyl- or alkynylphosphonic acid derivatives IIIa/IIIb .

11. A process for the preparation of substituted 2-phenylpyridines of the formula I where X is -CH=C(CN)- or -CH=C[CO-O-(C1-C4-alkyl)]-, which comprises reacting aromatic aldehydes of the formula VIa with phosphonic acid derivatives VIIa or VIIb .

12. A process for the preparation of substituted 2-phenylpyridines of the formula I where X is -CH=CH-, -CH=C(halogen)- or -CH=C(C1-C4-alkyl)-, which comprises reacting aldehydes of the formula VIa with anions VIIIa, VIIIb or VIIIc .

13. A process for the preparation of substituted 2-phenylpyridines of the formula I where X is -CH2-CH(CN)- or -CH2-CH[CO-O-(C1-C4-alkyl)]-, which comprises reacting phosphonic acid derivatives XVIa or XVIb with 3-pyridylbenzyl halides of the formula XVII

in the presence of a strong base.

14. A process for the preparation of substituted 2-phenylpyridines of the formula I where X is methylene and Y is oxygen, which comprises reactinq 3-pyridylbenzyl halides of the formula XVII

with trialkyl phosphites XII

P[ o~(C1-C4-alkyl)]3 XII.

15. A process for the preparation of substituted 2-phenylpyridines of the formula I where X is -CH2-O-CH2-, which comprises reacting 3-pyridylbenzyl halides of the formula XVII

with phosphonic acid derivatives XXIIa in the presence of a base.

16. A process for the preparation of substituted 2-phenylpyridines of the formula I where X is -O-CH2- and y, Z1 and Z2 are in each case oxygen, which comprises reacting phenols of the formula XXa with halomethyl thioethers XXIIa in the presence of a base, cleaving the reaction products XXIVa with a halogen and finally subjecting the cleavage products XXVa together with trialkyl phosphites XII

to an Arbuzov reaction.

17. A process for the preparation of substituted 2-phenylpyridines of the formula I where X is -CH=C(Cl)-, which comprises reacting aldehydes of the formula VIa with trichloromethanephosphonic acid derivatives XXVI

in the presence of an alkyllithium compound XXVII
(C1-C4-alkyl)-Li XXVII.

18. A process for the preparation of substituted 2-phenylpyridines of the formula I where Y, Z1 and Z2 are oxygen and R1 and R2 are hydrogen, which comprises either hydrolyzing compounds of the formula I where Y, Z1 and Z2 are in each case oxygen and R1 and R2 are in each case C1-C6-alkyl with a hydrohalic acid or first reacting compounds of the formula I
where Y, Z1 and Z2 are in each case oxygen and R1 and R2 are in each case C1-C6-alkyl with a tri(C1-C4-alkyl)silyl halide and then hydrolyzing the product with water.

19. A process for the preparation of substituted 2-phenylpyridines of the formula I where Y is oxygen, which comprises chlorinating compounds of the formula I, where Y, Z1 and Z2 are oxygen and R1 and R2 are hydrogen and subseguently reacting the products with nucleophiles HZ1R1 and/or HZ2R2.