Title of Invention	PROCESS FOR THE PRODUCTION OF SUBSTITUTED NICOTINIC ACID ESTERS
Abstract	The present invention relates to a process for the preparation of compounds of formula (I) wherein the substituents are as defined in claim 1, by reaction of a compound of formula (II) wherein R<sub>3</sub> is C<sub>1</sub>-C<sub>8</sub>alkyl or C<sub>3</sub>-C<sub>6</sub>cycloalkyl and R<sub>4</sub> and R<sub>05</sub> are as defined for formula (I), with a compound of formula (III) wherein R, R<sub>15</sub> R<sub>2</sub> and XI, are as defined for formula (I) in claim 1, in an inert solvent in the presence of a proton source.

Title of Invention

PROCESS FOR THE PRODUCTION OF SUBSTITUTED NICOTINIC ACID ESTERS

Abstract

The present invention relates to a process for the preparation of compounds of formula (I) wherein the substituents are as defined in claim 1, by reaction of a compound of formula (II) wherein R3 is C1-C8alkyl or C3-C6cycloalkyl and R4 and R05 are as defined for formula (I), with a compound of formula (III) wherein R, R15 R2 and XI, are as defined for formula (I) in claim 1, in an inert solvent in the presence of a proton source.

Full Text	PROCESS FOR THE PRODUCTION OF SUBSTITUTED NICOTINIC ACID ESTERS The present invention relates to a novel process for the preparation of 6-haloalkyl~3-nicotinic acid esters and also to novel enarnine intermediates for use in that process. 6-Haloalkyl-3-nicotinic acid esters are valuable intermediates for the preparation of herbicides such as those described, for example, in WO 01/94339. From Heterocycles, Vol. 48, No. 4,1998, pages 779-785 it is known to prepare 6-trifluoro-3-nicotinic acid ethyl esters substituted by aryl in the 4-position, corresponding to formula A, by means of dehydrogenation and subsequent oxidation of the compound of formula B in accordance with the following scheme As a result of the uneconomic multi-step procedure, that process is not well suited to the large-scale preparation of 6-haloalkyl-3-nicotinic 3cid ethyl esters. According to Heterocycles, Vol. 46,1997, pages 129-132, 6-trifluoro-3-nicotinic acid methyl esters substituted by phenyl or alkyl in the 2-position, corresponding to formula C, can be prepared by reacting a compound of formula E with a compound of formula D in benzene and in the presence of trifluoroacetic acid. In addition to unsatisfactory yields, SUBSTITUTE SHEET (RULE 26) that process has the serious disadvantage for large-scale preparation that the quality of the enamin'e (E) used as starting material continuously deteriorates during storage as a result of polymerisation reactions, making it considerably more difficult to ensure a consistent product quality. The problem of the present invention is consequently to make available a novel process for the preparation of 6-haloalkyl-3-nicotinic acid esters which makes it possible to prepare those compounds at reasonable cost, in high yields and with good quality. The present invention accordingly relates to a process for the preparation of compounds of formula I wherein R is d-Cealkyl; R05 is Hydrogen, d-C3alkyI, d-C3haloalkyl or Ci-C3alkyI-Ci-C3aIkoxy; Ri is a CrC6alkylene, C3-C6alkenylene or C3-C6alkynylene chain which may be substituted one or more times by halogen and/or by R5, the unsaturated bonds of the chain not being attached directly to the substituent Xi; R4 is CrC4haloalkyl; X1 is oxygen, -O(CO)-, -(CO)O-, -0(CO)0-, -N(R6)-0-, -0-NR17-, thio, sulfinyl, sulfonyl, -S02NR7-, -NR18S02-, -N(S02R18a)-, -N(R18b)C(0)- or -NR8-; R18a is C1-C6alkyl; R2 is hydrogen or C1-C8alkyI, or is a C1-C8a!kyI, C3-C6alkenyl or C3-C6alkynyl group which may be substituted one or more times by substituents selected from halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, CrC6alkoxy, d-C6alkoxycarbonyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyI, C2-C6haloalkynyI, C3-C6cycloalkyl, halo-substituted C3-C6cycloalkyl, C3-C6alkenyloxy, C3-C6alkynyloxy,C1-C6haloalkoxy, C3-C6haloalkenyloxy, cyano-C1-C6alkoxy, C1-C6aikoxy-C1-C6aIkoxy,C1-C6alkoxy-d-d>alkoxy-C1--C6alkoxy, C1-Cealkylthio-d-C6alkoxy, C1-C6alkylsulfinyl-C1-Ce-6alkoxy, d- C6alkylsulionyl-C1-C6alkoxy, C1-C6aIkoxycarbonyl-C1-C6alkoxy, C1-C6alkylcarbonyl, C1-C6aIkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylthio, C1-C6haloalkylsulfinyl, CrC6haloalkylsulfonyI, oxiranyl (which may in turn be substituted by C1-C6alkyl), (3-oxetanyl)oxy (which may in turn be substituted by C1-C6alkyl), benzyloxy, benzylthio, benzylsultinyl, benzylsulfonyl, Ci-C6alkylamino, di(C1-C6aikyI)arnino, R9S(0)20-, R10N(R11)SO2-, rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl and phenylsulfonyl; it being possible for the phenyl- or benzyl-containing groups to be in turn substituted by one or more C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy, halogen, cyano, hydroxy or nitro groups, or R2 is phenyl which may be substituted one or more times by C1-C6alkyI, C1-C6haloaIkyl, CrC6alkoxy, C-,-C6haloalkoxy, halogen, cyano, hydroxy or by nitro; or R2 is C3-C6cycloalkyl, d-C6alkoxy- or d-C6alkyl-substituted C3-C6cycloalkyl, 3-oxetanyl or CrC6alkyl-substituted 3-oxetanyl; or R2 is a three- to ten-membered, monocyclic or fused bicyclic, ring system which may be aromatic, partially saturated or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen, sulfur, and/or may contain the group -C(=0)-, -C(=S)-, -C(=NR19)-, -(N=0)-, -S(=0)- or -S02-, the ring system being attached to the substituent X1 either directly or by way of a d-dalkylene, C2-C4alkenylene, C2-C4alkynylene, -N(R12)-CrC4alkylene, -O-d-dalkylene, -S-d-dalkylene, -SO-CrC4alkylene or -S02-Ci-C4alkylene group and each ring system containing no more than 2 oxygen atoms and no more than two sulfur atoms, and it being possible for each ring system itself to be substituted one or more times by c1-C6alkyl, C1-C6haloalkyl, C1--C6alkenyl, C2-C6halo-alkenyl, C2-C6alkynyl, C^Cehaloalkynyl, Ci-C6aIkoxy, CrC6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, amino, hydroxy, CVQealkylthio, d-d>haloalkylthio, C3-C6-alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, CrC3alkoxy-CrC3alkylthio, d-C4alkyl-carbonyl-d-C3alkylthio, CrC4alkoxycarbonyl-Ci-C3alkylthio, cyano-CrC3alkylthio, Ci-C6-alkylsulfinyl, d-C6haloaIkylsulfinyl, d-C6alkylsulfonyl, CrC6haloalkylsulfonyl, amino-sulfonyl, CrC2alkylaminosulfonyl, N,N-di(CrC2alkyI)aminosulfonyl, di(C1-C4alkyl)amino, halogen, cyano, nitro or by phenyl, it being possible for the phenyl group to be in turn sQbstituted by hydroxy, CrC6alkylthio, d-C6haloalkylthio, C3-C6alkeny!thio, C3-C6halo-alkenylthio, C3-C6alkynylthio, d-C3alkoxy-d-C3alkylthio, CT-dalkylcarbonyl-d-dalkyl-thio, C1-C4alkoxycarbonyl-d C1-alkylthio, cyano-CrC3alkylthio,C1--C6alkylsulfinyl,C1-C6-haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsuIfonyl, aminosulfonyl, C1-C2alkyl- aminosulfonyl, N,N-C1i(C1-C2aIkyl)aminosulfonyl, C1i(C1-C4a!kyl)amino, halogen, cyano or by nitro, anC1 the substituents on nitrogen in a heterocyclic ring being other than halogen; R5 is hyC1roxy, C1-C6alkoxy, C3-C6cycloalkyloxy? C1-C6alkoxy-C1-C6alkoxy, C1-C6alkoxy-C-rC6alkoxy-C1-C6alkoxy or C1C2alky!sulfor]yloxy; Re, R7, Rs, R9, R10 Rn, R12, Ri7, R18 anC1 R18b are each inC1epenC1ently of the others hyC1rogen, C1-C6alkyl, C1C6ha)oalkyl, C1-C6alkoxycarbonyl, C1C6alkylcarbonyl, C1-C1r alkoxy-C1-C6alkyl, C-rC6alkoxy-C1C6alkyl substituteC1 by C1-C6a!koxy, benzyl, or phenyl, it being possible for phenyl anC1 benzyl to be in turn substituteC1 one or more times by C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy, halogen, cyano, hyC1roxy or by nitro; R6 not being hyC1rogen when R9 is hyC1rogen, C1-C6alkoxycarbonyl or C1C6alkylcarbonyl; or the group -R^X-pRa together is C1-C6alkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6-alkynyl, C2-C6haloalkynyl, C3-C6cycloalkyl, C^C1alkoxy, C1C6haloalkoxy, C1-C6alkylthio, C1-C6alky)sulfinyl, C1-C6alkyIsulfonyl, C1-C6haloalkyl, C1-C6haloalkylthio, C1-C1haloalkyl-sulfinyl, C1-C1shaloalkylsulfonyl, C1C6alkoxycarbonyl, C1-C1alkylcarbonyl, C1-C6alkylamino, C1i(C1-C6alkyl)amino, C1-C6alkylaminosutfonyl, C1i(C1~C6alkyl)aminosulfonyl, -NH-S-R13, -N-(C1C4aIkylthio)-Ri3, -NH-SO-R14, -N-(C1-C1alkylsulfonyl)-R14, -NH-SO2-R15, -N-(C1-C1alkyIsulfonyI)-R15, nitro, cyano, halogen, hyC1roxy, amino, formyl, rhoC1ano-C1-C6-alkyl, cyano-C1-C6alkyl, oxiranyl, C3-C6alkenyloxy, C3-C6aIkynyloxy, C1-C6alkoxy-C1-C6-alkoxy, cyano-C1-C6alkenyloxy, C1-C6alkoxycarbonyioxy-C1C1alkoxy, C3-C6alkynyloxy, cyano-C1-C6a!koxy, C1C6alkoxycarbonyl-C1-C6alkoxy, C1-C6alkylthio-C1-C1alkoxy, C1-C6alkoxycarbonyl-C-1-C6alkylthio, C1C6alkoxycarbonyl-C1-C6alkylsulfinyl, C1-C6alkoxycarbonyl-C1-C6alkylsulfonyLC1-C6alkylsulfonyloxy, C1-C6haloalkyIsulfonyloxy, phenyl, benzyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, benzylthio, benzylsulfinyl or benzylsulfonyl, it being possible for the phenyl groups to be substituteC1 one or more times by halogen, methyl, ethyl, trifluoromethyl, methoxy or by nitro; or the group -R1-X1-R2 together is a three- to ten-membereC1, monocyclic or fuseC1 bicyclic, ring system, which may be aromatic, partially saturateC1 or saturateC1 anC1 which may contain from 1 to 4 hetero atoms selecteC1 from nitrogen, oxygen anC1 sulfur anC1/or may contain one or two groups selecteC1 from -C(=0)-, -C(=S)-, -C(=NR20)-, -(N=0)-, -S(=0)-anC1 -S02-; the ring system either being attacheC1 to the pyriC1ine ring C1irectly via a carbon atom or being attacheC1 to the pyriC1ine ring via a carbon atom or via a nitrogen atom by way of a C1-C4alkylene, C2-C4alkenyl or C2-C4alkynyl chain, anC1 it being possible for each ring system to contain no more than 2 oxygen atoms anC1 no more than two sulfur atoms, anC1 it being possible for the ring, system itself to be substituteC1 one, two or three times by substituents selecteC1 from C1-C6alkyl, C1-C6haloaIkyI, C3-C6alkenyl, C3-C6haloa!kenyI, C3-C6alkynyl, C3-C6haloalkynyK C3-C6cycloaIkyl, hyC1roxy, C1-C6alkoxy, C1C6haloalkoxy, C3-C6alkenyloxy, C3-C6aIkynyloxy, mercapto, C1-C6alkylthio, C1-C6haIoalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynyIthio, C1-C1alkoxy-C1-C1alkylthio, C1-C3alkylcarbonyl-C1-C3aIkylthio, C1-C1alkoxycarbonyl-C1C1alkylthio, cyano-C1-C1alkylthio, C1C6aIkylsuIfinyl, C1-C1haloalkylsulfinyl, C1C6alkylsulfonyl, C1C6haloaIkylsulfonyl, aminosulfonyl, C1-C2aIkyIaminosulfonyl, C1i(C1C6alkyl)aminosulfonyl, C1-C3alkylene-R16, amino, C1-C6alkylamino, C1-C6alkoxyarnino, C1i(C1C6alky!)amino, (N-C1-C6alkyI)-C1-C6aIkoxyamino, halogen, cyano, nitro, phenyl, benzyloxy anC1 benzylthio, it being possible for phenyl, benzyloxy anC1 benzylthio to be in turn substituteC1 on the phenyl ring by C1 C3alkyl, C1-C3haloalkyl, C1-C1alkoxy, C1C3haloalkoxy, halogen, cyano or by nitro, anC1 substituents on a nitrogen atom in a heterocyclic ring being other than halogen; R13 is N(H)-C1-C6aIkyi, N(H)-C1C6alkoxy, ISKC1-C6a[kyl)-C1-C6aIkyI, N-(C1-C6alky()-C1-C6alkoxy, C1-C6alkoxy, C1-C6haloalkoxy, C1-C1>alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C3-C6cycloalkyl or phenyl, it being possible for phenyl to be in turn substituteC1 by C1-C3alkyl, C1C3haloalkyI, C1-C3alkoxy, C-i-Cshaloalkoxy, halogen, cyano or by nitro; R14 is N(H)-C1-C6alkyl, N(H)-C1C6alkoxy, N-(C1-C6aIkyI)-C1-C6alkyl, N-(C1-C6aIky!)-C1-C6alkoxy, C1-C1>a!koxy, C1-C6haloalkoxy, C1C6alkyl, C1-C6haloalkyl, C1-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C3-C6cycloalkyl or phenyl, it being possible for phenyl to be in turn substituteC1 by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1C3haloalkoxy, halogen, cyano or by nitro; R15 is N(H)-C1-C6alkyl, N(H)-C1-C6alkoxy, N-(C1C6alkyl)-C1C6alkyl, N-(C1-C6alkyi)-C1-C6alkoxy, C1-C6a)koxy, C1C6haloalkoxy, C1-C6alkyl, C1C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenylr C3-C6alkynyl, C3-C6haloalkynyl, C1-C6cycloalkyl or phenyl, it being possible for phenyl to be in turn substituteC1 by C1-C1alkyl, C1-C3haloalkyl, C1-C1alkoxy, C1-C3haloalkoxy, halogen, cyano or by nitro; R16 is C1-C3alkoxy, C2-G4a!koxycarbonyl, C1C3alkylthio, C1C1alkylsulfinyl, C1-C3alkyl-stilfonyl or phenyl, it being possible for phenyl to be in turn substituteC1 by C1-C3a!kyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or by nitro; anC1 Rt9 anC1 R2o are each inC1epenC1ently of the other hyC1rogen, hyC1roxy, C1-C6a!kyl, C1-C6haloalkyl, C1-C6alkoxy, cyano, C1-C6a!kylcarbonyI, C1-C6aIkoxycarbonyl or C1-C6alkylsulfonyl; which proC6ss comprises reacting a compounC1 of formula II wherein R3 is C1-C8alkyl or C3-C6cycloalkyl anC1 R4 anC1 R05 are as C1efineC1 for formula I, with a compounC1 of formula III wherein R, R17 R2 anC1 X-j are as C1efineC1 for formula I, in an inert solvent in the presenC6 ol a proton sourC6. The alkyl groups appearing in the substituent C1efinitions may be straight-chaineC1 or brancheC1 anC1 are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl anC1 octyl anC1 also the brancheC1 isomers thereof. Alkoxy, alkenyl anC1 alkynyl groups are C1eriveC1 from the mentioneC1 alkyl groups. The alkenyl anC1 alkynyl groups may be mono- or poly-unsaturateC1. Halogen is generally fluorine, chlorine, bromine or ioC1ine, preferably fluorine or chlorine. The same is also corresponC1ingly true for halogen in conjunction with other meanings such as haloalkyl or halophenyl. Haloalkyl groups preferably have a chain length of from 1 to 6 carbon atoms. Haloalkyl is, for example, fluoromethyl, C1ifluoromethyl, trifluoromethyl, chloromethyl, C1ichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-C1ifluoro-2r2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl or 2,2,2-trichloroethyl; preferably trichloromethyl, C1ifluorochloromethyl, C1ifluoromethyl, trifluoromethyl or C1ichlorofluoro-methyl. As haloalkenv! there come into consiC1eration alkenyl groups substituteC1 one or more times by halogen, halogen being fluorine, chlorine, bromine or ioC1ine, espeC1ally fluorine or chlorine, for example 2,2-C1ifluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyi, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl anC1 4,4,4-trifluoro-but-2-en-1-yl. Among the C3-C6alkenyl groups substituteC1 onC6, twiC6 or three times by halogen, preferenC6 is given to those that have a chain length of from 3 to 5 carbon atoms. As haloalkynyl there come into consiC1eration alkynyl groups substituteC1 one or more times by halogen, halogen being bromine, ioC1ine or, espeC1ally, fluorine or chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl anC1 4,4,4-trifluoro-but-2-yn-1-yl. Among the alkynyl groups substituteC1 one or more times by halogen, preferenC6 is given to those that have a chain length of from 3 to 5 carbon atoms. Alkoxy groups preferably have a chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, etboxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy or the pentyfoxy or hexyloxy isomers; preferably methoxy or ethoxy. Alkylcarbonyl preferably is aC6tyl or propionyl. Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxy-carbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl; preferably methoxycarbonyl or ethoxycarbonyl. Haloalkoxy groups preferably have a chain length of from 1 to 8 carbon atoms. Haloalkoxy is, for example, fluoromethoxy, C1ifluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-C1ifluoroethoxy or 2,2,2-trichloroetboxy; preferably C1ifluoromethoxy, 2-chlorethoxy or trifluoromethoxy. Alkylthio groups preferably have a chain length of from 1 to 8 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio. Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec~buty!suifinyl or tert-butylsulfinyl; preferably methylsulfinyl or ethylsulfinyl. Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropyl-sulfonyl, n-butylsulfonyl, isobutylsylfonyl, sec-butylsulfonyl ortert-C1utylsulfonyl; preferably methylsulfonyl or ethylsulfonyi. Alkoxyalkoxy groups preferably have a chain length of from 1 to 8„ carbon atoms. Examples of alkoxyalkoxy are: methoxymethoxy, methoxyethoxy, methoxypropoxy, ethoxyrnethoxy, ethoxyethoxy, propoxymethoxy anC1 butoxybutoxy. Alkylamino is, for example, rnethylamino, ethylamino, n-propylamino, isopropylamino or the butylamine isomers. C1ialkylamino is, for example, C1imethylamino, methylethylamino, C1iethylamino, n-propylmethylamino, C1ibutylamino or C1iisopropylamino. PreferenC6 is given to alkylamino groups having a chain length of from 1 to 4 carbon atoms. Alkoxyalkyl groups preferably have a chain length of from 2 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethy), n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl. Alkylthioalkyl groups preferably have from 2 to 8 carbon atoms. Alkylthioalkyl is, for example, methyl-thiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propyl-thioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl. The cycloalkyl groups preferably, have from 3 to 8 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl anC1 cyclooctyl. Phenyl, incluC1ing phenyl as part of a substituent such as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl anC1 phenoxyalkyl, may be present in substituteC1 form, in which case the substituents may be in the ortho-, meta- anC1/or para-position(s). PreferreC1 substituent positions are the positions ortho anC1 para to the ring attachment position. In accorC1anC6 with the proC6ss accorC1ing to the invention there are preferably prepareC1 those compounC1s of formula I wherein R4 is halomethyl or haloethyl; Ros is hyC1rogen; X, is oxygen, -O(CO)-, -(00)0, -0(C0)0-, -N(R6)-0-, -0-NR17-, thio, sulfinyl, sulfonyl, -S02NR7-, -NR18S02- or -NR8-; R2 is hyC1rogen or C1-C6alky), or a C1C6aikyl, C3-C6alkenyl or C3-C6alkynyi group which is substituteC1 one or more times by halogen, hyC1roxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, C1-C6alkoxy, C1-C6alkoxycarbonyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6-alkynyl, C2-C6ha)oalkynyl, C3-C6cycloaIkyl, halo-substituteC1 C3-C6cycloaikyl, or by C3-C6alkenyloxy, C3-C6alkynyloxy, C1-C6haloalkoxy, C3-C6haloaIkenyloxy, cyano-C1C6aIkoxy, C1-C6aikoxy-C1C6alkoxy, C1C6alkoxy-C1C6alkoxy-C1C6alkoxy, C-i-C6alkyl-thio-C1-C6alkoxy, C1-C6alkylsuIfinyl-C1C6alkoxy, C1-C6alkylsulfonyl-C1-C6alkoxy, Ct-C6-alkoxycarbonyl-C1-C6alkoxy, C1-C6alkoxycarbonyl, C1-C6alkylcarbonyl, C1-C6alkylthio, C1C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylthio, C1C6haloalkylsulfinyl, C1C6-haloalkylsujfonyl, oxiranyl (which may in turn be substituteC1 by C-rC6alkyI), or by (S-oxetanyl)oxy (which may in turn be substituteC1 by Cn-C6alkyl), or by benzylthio, benzylsulfinyi, benzylsulfonyl, C1-C$alkylamino, C1i(C-i-C6alkyl)amino, R9S(0)20-, RioN(Rn)S02-, rhoC1ano, phenyl, phenoxy, phenylthio, phenylsulfiny! or by phenylsulfonyl; it being possible for the phenyl- or benzyl-containing groups to be in turn substituteC1 by one or more C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy, halogen, cyano, hyC1roxy or nitro groups, or R2 is phenyl which may be substituteC1 one or more times by C1C6alkyl, C1C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy, halogen, cyano, hyC1roxy or by nitro; or R2 is C3-C6cycloalkyl, C1C6alkoxy- or C1-C6alkyl-substituteC1 C3-C6cycloalkyl, 3-oxetanyl or C1C6alkyl-substituteC1 3-oxetanyl; or R2 is a five- to ten-membereC1, monocyclic or fuseC1 bicyclic, ring system which may be aromatic, partially saturateC1 or fully saturateC1 anC1 may contain from 1 to 4 hetero atoms selecteC1 from nitrogen, oxygen, sulfur, anC1/or may contain the group -C(=0)-, -C(=S)-, -C(=NR19)-, -(N=0)-, -S(=0)- or -S02-, the ring system being attacheC1 to the substituent Xi C1irectly or by way of a C1-C1alkylene, C2-C4alkenyl-C1-C4alkylene, C2-C4alkynyl-C1-C4alkylene, -N(R-i2)-C1-C4aIkylene, -SO-C1C4alkylene or -S02~C1-C4alkylene group anC1 each ring system containing no more than 2 oxygen atoms anC1 no more than two sulfur atoms, anC1 it being possible for each ring system itself to be substituteC1 one or more times by C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C1-C6a!koxy, C1-C6haloa!koxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, amino, hyC1roxy, C1C6alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6halo-alkenylthio, C3-C6alkynylthio, C1-C3alkoxy-C1-C3alkylthio, C1-C4alkylcarbonyl-C1-C3aIkyl-thio, C1-C4alkoxycarbonyl-C1C3alkylthio, cyano-C1-C3alkylthio, C1C6alkylsulfinyl, C1C6haloalkylsulfinyl, C1-C6alky!sulfonyI, C1C6haloaIkylsulfonyl, aminosulfonyl, C1C2alkylaminosulfonyI, N)N-C1i(C1-C2alkyl)aminosulfonyl, C1i(C1C4alkyl)amino, halogen, cyano, nitro or by phenyl, it being possible for the phenyl group to be in turn substituteC1 by hyC1roxy, C-,-C6alkylthio, C1C6haloalkylthio, C3-C6alkenylthio, C1C6haloalkenyithio, CVC6alkynyIthio, C1C3alkoxy-C1»C3alkylthio, C1C4aIkyIcarbonyI-C1C3alkylthio, C1-C1-alkoxycarbonyl-C1C3alkylthio, cyano-C1-C3alkylthio, C1-C1>alkylsulfinyl, C1C6haloalkyl-suifinyi, C1C6alkylsulfonyl, C1-G6haIoaIkyIsulfonyl, aminosulfonyl, C1C2alkyIaminosulfonyl, N,N-C1i(C1C2alkyl)aminosuIfonyl, di(C1-C4alky!)amino, halogen, cyano or by nitro, anC1 the substituents on nitrogen in a heterocyclic ring being other than halogen; R6) R7, R8, R9, R10 R11, R12, R17 anC1 R18 are each inC1epenC1ently of the others hyC1rogen, C1C1aIkyl,C1-C6haloalkyl, C1-C6alkoxycarbonyl, C1-C6alkylcarbonyl, C1-C6a!koxy-C1C6aIkyl, C1-C6alkoxy-C1-C6alkyl substituteC1 by C-rC6aIkoxy, benzyl, or phenyl, it being possible for phenyl anC1 benzyl to be in turn substituteC1 one or more times by C1-C6alkyl, C1-C6haloalkyl, C1C6alkoxy, C1-C6haloalkoxy, halogen, cyano, hyC1roxy or by nitro; R6 not being hyC1rogen when R9 is hyC1rogen, C1-C6alkoxycarbonyl or C1C6alkylcarbonyl; or the group -R-rX^Rg together is C1C6alkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6-alkynyl, C2-C6haloaIkynyl, C3-C6cycloaIkyI, C1-C1alkoxy, C1-C6haloalkoxy, C1C6alkylthio, C1-C6alkyIsu!finyl, C1-C6alkylsulfonyl, C1-C6haloalkyl, C1-C6haloalkylthio, C1-C6haloalkyl-sulfinyl, C1C6haloalkylsulfonyl, C1-C6alkoxycarbonyl, C1-C6alkylcarbonyl, C1-C6alkylamino, C1i(C1C6alkyl)amino, C1-C6alkylaminosulfonyl, C1i(C1-C6alkyI)aminosulfonyl, -NH-S-R13, -N-(C1-C1alkyithio)-R13, -NH-SO-R14, -N-(C1C1alkylsulfonyl)-R14, -NH-S02-R15, -N-(C1-C1alkyIsulfonyl)-R15, nitro, cyano, halogen, hyC1roxy, amino, formyl, rhoC1ano-C1-C6aIkyl;cyano-C1-C6alkyl, oxiranyl, C3-C6alkenyloxy, C1-C6alkynyloxy, C1-C6alkoxy-C1-C1alkoxy, cyano-C1-C6alkenyloxy, C1-C6alkoxycarbonyloxy-C1-C6alkoxy, C1-C6alkynyI-oxy, cyano-C1-C6aIkoxy, C1-C6alkoxycarbonyl-C1-C6alkoxy, C1-C6alkylthio-C1-C6alkoxy, alkoxycarbonyl-C1C6alkylthio, alkoxycarbonyl-C1C6alkylsulfinyl, alkoxycarbonyl-C1-C6alkylsuIfonyl, C1-C6alkylsulfonyloxy, C1-C6haloalkylsulfonyloxy, phenyl, benzyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, benzylthio, benzylsulfinyl or benzylsulfonyl, it being possible for the phenyl groups to be substituteC1 one or more times by halogen, methyl, ethyl, trifluoromethyl, methoxy or by nitro; or the group -R1-X-R2 together is a five- to ten-membereC1, monocyclic or fuseC1 bicyclic, ring system, which may be aromatic or partially saturateC1 anC1 which may contain from 1 to 4 hetero atoms selecteC1 from nitrogen, oxygen anC1 sulfur, the ring system either being C1irectly attacheC1 to the pyriC1ine ring or being attacheC1 to the pyriC1ine ring by way of a C1C1alkylene group, anC1 it being possible for each ring system to contain no more than 2 oxygen atoms anC1 no more than two sulfur atoms, anC1/or to contain the group -C(=0)-, -C(=S)-, -C(=NR2o)-, -(N=0)-, -S(=0)- or -S02-; anC1 the ring system itself may be substituteC1 one, two or three times by C1-C6alkyl, C1-C6-haloalkyl, C3-C6alkenyl, C3-C6haloaIkenyl, C3-C6alkynylf C3-C6haloalkynyl, C1C6alkoxy, C1-C6ha!oa!koxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, C1-C6alkyIthio, C1-C6-haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C2-C5alkoxyalkyl-thio, C1-C5aC6tylalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C1cyanoalkylthio, C1-C6a!kyl-sulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl, C1-C2alkylaminosulfonyl, C2-C4C1ialkyIaminosuIfonyi, C1C3alkylene-R16, N(H)-C1-C6aIkyI, N(H)-C1-C6alkoxy, N-(C1-C6aikyl)-C1-C6alkyl, N-(C1-C6alkyI)-C1-C6alkoxy, halogen, cyano, nitro, phenyl anC1 by benzylthio, it being possible for phenyl anC1 benzylthio to be in turn substituteC1 on the phenyl ring by C1-C1?alkyl> C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or by nitro, anC1 substituents on nitrogen in a heterocyclic ring being other than halogen; anC1 R19 anC1 R20 are each inC1epenC1ently of the other hyC1rogen, hyC1roxy, C1-C6alkyl, C1-C6-haloalkyl, C1-C6alkoxy, C1-C6alkylcarbonyl, C1-C6alkoxycarbonyl or C1-C6alkylsulfonyl. The proC6ss accorC1ing to the invention is espeC1ally suitable for the preparation of those compounC1s of formula I wherein Ri is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CF2-, -CH=CHCHr, -CH(CH3)- or -OCCH2-, but preferably -CH2-, the free valency on the left in each case being attacheC1 to the pyriC1ine ring. PreferenC6 is furthermore given to the preparation of those compounC1s of formula I wherein X1 is oxygen, sulfonyl or a group -NR18S02-, espeC1ally oxygen. In accorC1anC6 with the proC6ss accorC1ing to the invention, speC1al preferenC6 is given to the preparation of those compounC1s of formula I wherein R2 is CH3, CH2CH3, CH2OCH3, CH2OCH2CH3, CH2CH2OCH3, CH2CH2OCH2CH3, CH2CF3, propargyl, cyclopropylmethyl, benzyl, CH2CH2S02CH3 or CH2CH2OCH2CH2OCH3, but preferably CH2CH2OCH3, with very speC1al preferenC6 being given to those compounC1s wherein Xi is oxygen anC1 R-, is -CHr. In accorC1anC6 with the proC6ss accorC1ing to the invention, preferenC6 is given to the preparation of those compounC1s of formula I wherein R05 is hyC1rogen, CH3, CH2C1, CH2Br or CH2OCH3) but espeC1ally hyC1rogen. From that group, those compounC1s wherein R is ethoxy or methoxy may be prepareC1 espeC1ally aC1vantageously. Furthermore, in accorC1anC6 with the proC6ss accorC1ing to the invention there may be aC1vantageously prepareC1 compounC1s of formula I wherein R2 is inC1icateC1 ip those preferreC1 meanings of R2, as in the case of, for example, ° , the attachment position is at the carbon atom markeC1 "CHFurthermore, there may also be aC1vantageously prepareC1 those compounC1s wherein the group -FVX1-R2 together is a four- to ten-rnembereC1, monocyclic or fuseC1 tricyclic, ring system, which may be aromatic, partially saturateC1 or saturateC1 anC1 contains from 1 to 4 hetero atoms selecteC1 from nitrogen, oxygen anC1 sulfur anC1/or contains one or two groups selecteC1 from -C(=0)-, -C(=S)-, -C(=NR2o)- anC1 -S02-, the ring system being attacheC1 to the pyriC1ine ring via a carbon atom or preferably via a nitrogen atom by way of a C1-C4alkylene chain, espeC1ally a methylene chain. Among such ring systems speC1al mention may be maC1e of the following preferreC1, four- to seven-membereC1 ring systems attacheC1 via a nitrogen atom to the methylene group, the attachment position being shown in each case at the bottom left: wherein r is 0, 1 or 2; R51l R53, R56 anC1 R65 are each inC1epenC1ently of the others hyC1rogen, halogen, C1-C6alkyl, C1-C6haloalkyl, C3-C6cycloalkyl, C3-C6alkenyl, C3-C6alkynyl, C1-C3alkoxy-C1-C3aIkyl, C1-C1alkoxy, C3-C6alkenyloxy, C3-C6aIkynyloxy, C1C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C3-C6aIkenyIthio or C3-C6aIkynylthio; R52 is hyC1rogen, C1-C6alkyI, C1-C6haloalkyl, C3-C6cycloalkyi, C3-C6alkenyl, C3-C6alkynyl, C1-C6aIkoxy, amino, or phenyl which may in turn be substituteC1 by R70; R54, R55 anC1 R60 are each inC1epenC1ently of the others hyC1rogen, C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6alkynyl or C3-C6cycloalkyI; R57, R63, Res, R67, Res anC1 R69 are each inC1epenC1ently of the others C1-C6alkyI, or phenyl which may in turn be substituteC1 by R70; Re4 is C1C6alkyl, C1-C6haloalkyl, C3"C6cycloalkyl, C3-C6alkenyl, C3-C6alkynyl, or phenyl which may in turn be substituteC1 by R7o; R58 anC1 R61 are hyC1rogen, halogen, C1-C6alkyl or C^C6haloalkyl; R59 is C1-C6alkyl, C1-C6haloalkyl, C1-C3a!koxy-C1-C3alkyl, C3-C6alkenyl or C3-C6alkynyi; R62 is hyC1rogen, C1-C6alkyl, C1-C1alkoxycarbonyl or C1-C4alkylthiocarbonyI; or R51 together with Rs2, or R54 together with an aC1jaC6nt group R56, or R58 together with an aC1jaC6nt group R59, or R60 together with an aC1jaC6nt group R61, or, when r is 2, two aC1jaC6nt groups R56 or two aC1jaC6nt groups R61 together may form a saturateC1 or unsaturateC1 C1-C5aIkylene or C3-C4alkenylene briC1ge, which may in turn be substituteC1 by a group R70 or interrupteC1 by oxygen, sulfur or nitrogen; each R7o is inC1epenC1ently halogen, C1-C3alkyl, CVCahaloalkyl, hyC1roxy, C1C3alkoxy, C1-C3haloalkoxy, cyano or nitro; X is oxygen, sulfur or NR6; X3, X4 anC1 X5 are oxygen or sulfur; X6 anC1 X7 are oxygen, sulfur, S(O) or S02; anC1 X8 is CH2, oxygen, sulfur, S(O), S02 or MR71, wherein R71 is hyC1rogen or C1-C6alkyl. In the context of the present invention, preferenC6 is given to the group R^X^Ra together being C1C6alkyl, C1-C6haloaIkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6halo-alkynyl, C3-C6cycloalkyl, C1C6alkoxy or C1-C6alkylthio, e.g. methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, fluoromethyl, 2-fluoroethyl, C1ifluoroethyl, trifluoroethyl, vinyl, i-propenyl, methoxy, ethoxy, methylthio or ethylthio. In the context of the present invention, preferenC6 is given to R being methyl, ethyl, n-propyl or isopropyl, espeC1ally ethyl. R3 is preferably methyl or ethyl, very espeC1ally ethyl. R4 is preferably trifluoromethyl, C1ifluoromethyl, chloroC1ifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, espeC1ally trifluoromethyl, chloroC1ifluoromethyl or C1ifluoromethyl. As inert solvents for the methoC1 accorC1ing to the invention there are suitable, for example, aromatic solvents such as benzene, chlorobenzene, fluorobenzene, xylenes, toluene, or alcohols such as methanol or ethanol, anC1 also ethyl aC6tate, aC6tonitrile, C1imethyl sulfoxiC1e, C1imethylformamiC1e, C1imethylaC6tamiC1e, N-methyl-2-pyrroliC1one, aC6tone, butanone, halogenateC1 solvents such as, for example, methylene chloriC1e, trichloro-methane, C1ichloroethylene or trichlorethane, ethers such as tetrahyC1rofuran, C1iethyl ether, 1,2-C1imethoxyethane, C1ioxane or methyl tert-butyl ether. Ethanol anC1 toluene are espeC1ally preferreC1. Organic or mineral aC1C1s are suitable as the proton sourC6. Examples of suitable proton sourC6s are HC1, HBr, H2S04, carboxylic aC1C1s such as aC6tic aC1C1 anC1 C1erivatives thereof such as trifluoroaC6tic aC1C1 anC1 trichloroaC6tic aC1C1, sulfonic aC1C1s such as methane-sulfonic aC1C1 or p-toluenesulfonic aC1C1 anC1 also carbonic aC1C1. As the proton sourC6 for the proC6ss accorC1ing to the invention speC1al preferenC6 is given to trifluoroaC6tic aC1C1. The reactions can be carrieC1 out at ambient temperature or at elevateC1 temperature. In general, aC1C1ition of the reactants is carrieC1 out at a temperature from ambient temperature to the boiling point of the solvent, espeC1ally from 20 to 140°C, preferably from 40 to 120°C, with subsequent heating of the reaction mixture, aC1vantageously to the boiling point of the solvent. The compounC1s of formula II are known or are acC6ssible by known methoC1s. ProC6sses for the preparation of compounC1s of formula II are C1esC1ibeC1, for example, in J. Org Chern. (1995) vol 95, 3523, in H. Amil, T. Kobayashi, H. Terasawa, K. Uneyama, Org. Lett. 3(20), 3103-3105 (2001) anC1 also A. Colla, G. Clar, S. Krimmer, P. Fischer, M.A.P. Martins, Synthesis-Stuttgart (6),483-486 (1991). Some of the compounC1s of formula III are known. The preparation of such compounC1s is C1esC1ibeC1 in H. G. O. Becker, J. Prakt. Chem. (1961), Vol 12, 294., in WO 00/24714 anC1 also in C1.H. Wu, W. Wang, J. LabelleC1 CompC1. RaC1 39(2),105-107(1997). The compounC1s of formula III wherein -FVX1-R2 is -CH2-0-CH2-CH2-0-CH3, that is to say compounC1s of formula Ilia wherein R is as C1efineC1 for formula 111, are novel anC1 were C1evelopeC1 speC1fically for the preparation of compounC1s of formula I, anC1 the present invention accorC1ingly relates thereto. In a preferreC1 compounC1 of formula Ilia, R is methyl or ethyl. CompounC1s of formula III can be prepareC1 using proC6sses known to the person skilleC1 in the art, for example by reacting the unsaturateC1 ketones on which they are baseC1 with ammonia gas as C1esC1ibeC1 in Preparation Example P1 hereinbelow. In a preferreC1 emboC1iment of the proC6ss accorC1ing to the invention, the starting compounC1s of formula III are prepareC1 from the 3-oxo-carboxyIic aC1C1 esters on which they are baseC1 by introC1uC1ng ammonia gas anC1 then, without further isolation, reacting C1irectly with the compounC1s of formula II. That proC6ss is espeC1ally aC1vantageous for the large-scale preparation of compounC1s of formula I. in The compounC1s of formula I either may be useC1 C1irectly in the reaction mixture for further reactions or alternatively may be isolateC1. Isolation of the compounC1s of formula I can be carrieC1 out, for example, by extraction of the reaction mixture anC1 subsequent removal of the solvent from the proC1uct-containing phase by customary methoC1s. The proC6ss accorC1ing to the invention will be explaineC1 in greater C1etail in the following Preparation Examples: Example Pi: Preparation of 3-amino-4-methoxvethoxv-but-2-enoic aC1C1 ethyl ester: A mixture of 1.37 g (6 mmol) of 3-oxo-4-methoxyethoxy-butanoic aC1C1 ethyl ester (1) in 13 ml of ethanol is introC1uC6C1 into a reaction vessel anC1 cooleC1 to a temperature of 0°C using an iC6/water bath. Ammonia gas is then introC1uC6C1 for a perioC1 of 30 minutes, with stirring, anC1 the reaction mixture is stirreC1 for a further 20 minutes at a temperature of 0°C. After removing the cooling bath, the reaction mixture is alloweC1 to warm up to a temperature of 20°C anC1 ammonia gas is then introC1uC6C1 for a further hour. The reaction mixture is then stirreC1 for 20 hours. After removal of the solvent in vacuo, there are obtaineC1 1.3 g (95 % of theory) of 3-amino-4-methoxyethoxy-but-2-enoic aC1C1 ethyl ester (2) in the form of an orange-coloureC1 oil. 1H NMR (CC1Cl3): 1.30 (t, 3H, CH3CH20-), 3.40 (s, 3H, CH30-), 3.55 (m, 2H, OCHsCHsO), 3.60 (m, 2H, OCH2CH2O), 4.10 (s, 2H, C=CC1i>0-), 4.15 (q, 2H, CH3Ch2O-), 4.50 (s, 1H, CH=CNH2). 13C NMR (CC1C13): 14.7 (CH3), 58.9 (CH2), 59.2 (CH3), 70.0 (CH2), 71.0 (CH2), 71.8 (CH2), 81.9 (CH),,159.7 (C), 170.3 (C) . MS: 203 (M+), 158, 157, 144,129, 114, 100, 98, 83, 71, 59, 45. Example P2: Preparation of 2-methoxvethoxvmethyl-3--ethoxvcarbonvl-6-trifluoromethvl-pyriC1ine (4): A mixture of 52.3 g (0.24 mol) of 3-oxo-4-methoxyethoxy-butanoic aC1C1 ethyl ester (1) in 150 ml of toluene is introC1uC6C1 into a reaction vessel equippeC1 with a water separator. Ammonia gas is then introC1uC6C1 into the reaction mixture for 2 hours, with stirring. Refluxing is then carrieC1 out for 30 minutes anC1 the water is collecteC1 in the separator. After cooling the reaction mixture to a temperature of 20°C, the proC6C1ure is repeateC1. Ammonia gas is again introC1uC6C1 for 1.5 hours, with stirring, anC1 the reaction mixture is then refluxeC1 in orC1er to separate off the water. After cooling the reaction mixture, which contains 3-amino-4-methoxyethoxy-but-2-enoic aC1C1 ethyl ester (2), to a temperature of 20°C, 48 g (0.248 mol) of 1 -ethoxy-3-oxo-4-tnfliiorobutene (3) are aC1C1eC1 anC1 stirring is carrieC1 out at a temperature of 20°C for 18 hours. 1.5 ml of trifluoroaC6tic aC1C1 are then aC1C1eC1, stirring is carrieC1 out at a temperature of 20°C for 2 hours anC1 refluxing is carrieC1 out for a further 2 hours. The reaction mixture is then alloweC1 to cool C1own to a temperature of 20°C anC1 is then washeC1 with 100 ml of 1M NaHC03. The aqueous phase is separateC1 off anC1 is then extracteC1 with 150 ml of toluene anC1 the combineC1 organic phases are then C1rieC1 over MgS04. After removal of the solvent in vacuo, there are obtaineC1 65.4 g (62 % of theory) of 2-methoxyethoxymethyl-3-ethoxyGarbonyl-64rifluoromethylpyriC1ine in the form of a C1ark-brown oil. 'H NMR (CC1C13): 1.40 (t, 3H, CH3CH2O-), 3.35 (s, 3H, CH3O-), 3.55 (m, 2H, OCH2CH2O), 3.70 (m, 2H, OCH2CH2O), 4.45 (q, 2H, CH3CH2O-), 5.00 (s, 2H, ArCH2O-), 7.70 (s, 1H, ArH), 8.30 (s,1H, ArH). MS: 307 (M+), 262, 248, 233, 204, 202,161, 128, 109, 59, 45 The other compounC1s listeC1 in Table 1 can also be prepareC1 in that manner. In the following Table, the valency on the left of the raC1ical F^ is attacheC1 to the pyriC1ine ring. When no free valency is inC1icateC1 in the case of the substituent R2, as in the case of, for example, , the attachment position is at the carbon atom markeC1 WCHH. Table 1: CompounC1s of formula la wherein R is methyl or ethyl: What is claimed is: 1. A process for the preparation of a compound of formula I wherein R is C1-C6alkyl; R05 is Hydrogen, C1-C3alkyl, C1-C3haloalkyl or C1-C3alky)-C1-C3alkoxy; Ri is a Ci-C6alkylene, C3-C6alkeny/ene or C3-C6alkynylene chain which may be substituted one or more times by halogen and/or by R5, the unsaturated bonds of the chain not being attached directly to the substituent Xr, R4 is Ci-C4haloalkyI; X1 is oxygen, -O(CO)-, -(CO)O-, -0(CO)0-, -N(R6)-0-, -ONR17-, thio, suifinyl, sulfonyl, -S02NR7-, -NR18S02-, -N(S02R18a)-, -N(R18b)C(0)- or -NR8-; Ri8a is C1-C6alkyl; R2 is hydrogen or C1-C8alkyl, or is a C1-C8aIkyl, C3-C6alkenyl or C3-C6alkynyl group which may be substituted one or more times by substituents selected from halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, C1-C6alkoxy, CrC6alkoxycarbonyl, C2-C6a)kenyl, C2-C6haloalkenyI, C2-C6alkynyl, C2"C6haloalkynyl, C3~C6cycioalkyl, halo-substituted C3-C6cycloalkyl, C3-C6aIkenyioxy, C3-C6aIkynyloxy, CrC6hafoaIkoxy, C3» C6haloaikenyloxy, cyano-C1-C6a!koxy, C1-C6alkoxy-Cr-C6alkoxy, C1-C6alkoxy-C1-C6alkoxy-C1-C6alkoxy, C1-C6alkylthio-C1-C6alkoxy,C1 -C6alkylsulfinyl-C1-C6alkoxy, G,-C6alkylsulfonyl-Cr-C6alkoxy, Cr-C6alkoxycarbonyl-C1-C6alkoxy, C1-C6alkylcarbonyl, C1-C6alkyIthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylthio, C1-C6haloalkylsulfinyl, C1-C6haloalkylsulfonyl, oxiranyl (which may in turn be substituted by C-rC6alkyl), (3-oxetanyI)oxy (which may in turn be substituted by Ci-C6alkyl), benzyloxy, benzylthio, benzylsulfinyl, benzylsulfonyl, CVCealkylamino, di(CrC6alkyI)amino, R9S(0)20-, R10N(R11)S02-, rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl and phenylsulfonyl; it being possible for the phenyl-.or benzyl-containing groups to be in turn substituteC1 by one or mora C1-C6alkyl, C1-C6haloalkyl, c1-C6alkoxy, C1-C6haloalkoxy, halogen, cyano, hyC1roxy or nitro groups, or R2 is phenyl which may be substituteC1 one or more times by C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy, halogen, cyano, hyC1roxy or by nitro; or R2 is C3-C6cycloalkyl, C1-C6alkoxy- or C1--C6alkyl-substituteC1 C3-C6cycloalkyI, 3-oxetanyl or C1-C6alkyl-substituteC1 3-oxetanyl; or R2 is a three- to ten-membereC1, monocyclic or fuseC1 bicyclic, ring system which may be aromatic, partially saturateC1 or fully saturateC1 anC1 may contain from 1 to 4 hetero atoms selecteC1 from nitrogen, oxygen, sulfur, anC1/or may contain the group -C(=0)-, -C(=S)-, -C(=NR19)-,.-(N=0)-, -S(=0)- or -S02-, the ring system being attacheC1 to the substituent Xi either C1irectly or by way of a Ci-C4alkylene, C2-C4alkenylene, C2-C1aIkynylene, -N(R12)-C1-C1aIky)ene, -O-C1-C1alkylene, -S-Ci-C4alkylene, -S0-C1-C4alkylene or -S02-C1-C4aIkyIene group anC1 each ring system containing no more than 2 oxygen atoms anC1 no more than two sulfur atoms, anC1 it being possible for each ring system itself to be substituteC1 one or more times by C1-C6alkyi, C1C6haloalkyl, C2-C6alkenyl, C2-C6halo-alkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C1-C6alkoxy, Ci-C6haloaIkoxy, C3-C6alkenyloxy, C3-C6alkynyIoxy, mercapto, amino, hyC1roxy, C1-C1>alkyIthio, C1-C6haloa!kylthio, C3-C6-alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C-rC3alkoxy-C1-C1alkylthio, C1-C4alkyI-carbonyl-C1-C3alkylthio, C1-C1alkoxycarbonyl-C1-C3alkylthio, cyano-C1-C3alkylthio, C1-C6-alkylsulfinyl, C1-C6haloalkylsulfinyI, C1-CealkylsuIfonyl, C1-C6haloalkylsulfonyl, amino-sulfonyl, C1-C2a!kylaminosulfonyl, N,N-C1i(C1-C2alkyI)aminosulfonyI, C1i(C1-C1alkyI)amino, halogen, cyano, nitro or by phenyl, it being possible for the phenyl group to be in turn substituteC1 by hyC1roxy, C1-C6alkyIthio, C1-C1>haloalkylthio, C3-C6alkenylthio, C3-C6halo-alkenylthio, C3-C6aIkynylthio, C1C3alkoxy-C1-C3alkyIthio, C1-C1a!kylcarbonyl-C1-C3alkyl-thio, C1C4alkoxycarbonyl-C1C3aIkylthio, cyano-C1-C3alkylthio, C1C1alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6alkylsulfonyl, C1C6haloaIkylsu!fonyl, aminosulfonyl, C1-C2alkyl-aminosulfonyl, N,N-C1i(C1-C2alkyl)aminosulfonyl, C1i(C1-C4alkyl)amino, halogen, cyano or by nitro, anC1 the substituents on nitrogen in a heterocyclic ring being other than halogen; R5 is hyC1roxy, C1-C6alkoxy, C3-C6cycIoaIkyloxy, C1-C6alkoxy-C1-C6alkoxy, C1-C6a!koxy-C1-C6aIkoxy-C1-C6alkoxy or C1-C2aIkylsulfonyioxy; Re, R-, RB, RQ, R10 R11, RI2, R17, RIS anC1 R18b are each inC1epenC1ently of the others hyC1rogen, C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxycarbonyI, C1-C6alkylcarbonyl, C1-C6-alkoxy-Ci-C6alkyl, C1-C6alkoxy-C1-C6alkyI substituteC1 by C1-C6alkoxy, benzyl, or phenyl, it being possible for phenyl anC1 benzyl to be in turn substituteC1 one or more times by C1.-C6alkyl,,C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloa!koxy, halogen, cyano, hyC1roxy or by nitro; R6 not being hyC1rogen when R9 is hyC1rogen, C1-C6alkoxycarbonyl or C1-C6alkyI-carbonyl; or the group -RrX1-R2 together is C1-C6alkyl, C2-C6alkenyl, C2-C6haloaIkenyl, C2-C6-alkynyl, C2-C6haloaIkynyI, C3-C6cycloalkyl, C1-C6alkoxy, C1C6haloalkoxy, C1-C6alkylthio, C1-C6aIkylsulfinyl, C1-C6alkylsu!fonyl, C1-C6haloa!kyl, C1-C6haloa!kyIthio, C1-C6haloalkyI-sulfinyl, C1-C6haloalkylsulfonyl, C1-C6alkoxycarbonylf C1C6aIkylcarbonyl, C1-C6alkylamino, C1i(C1-C6alkyl)amino, C1-C6alkylaminosulfonyl, C1i(C1-C6alkyl)aminosulfonyl, -NH-S-R13, -N-(C1-C1alky(thio)-R13, -NH-SO-R14, -N-(C1-C4alkylsulfonyl)-R14, -NH-S02-R15, -N-(C1-C4alkylsulfonyl)-Ri5, nitro, cyano, halogen, hyC1roxy, amino, formyl, rhoC1ano-C1-C6-alkyl, cyano-C1-C6alkyl, oxiranyl, C3-C6alkenyloxy, C3-C6alkynyloxy, C1-C6alkoxy-C1-C1r alkoxy, cyano-C1-C6alkenyloxy, C1-C1alkoxycarbonyloxy-C1-Cealkoxy, C3-C6alkynyloxy, cyano-C1-C6alkoxy, C1-C6alkoxycarbonyl-C1-C1ialkoxy, C1-C1>alkylthio-C1-C6aikoxy, C1-C6alkoxycarbonyl-C1-C6alkylthio, C1-C1aIkoxycarbonyKXrC1>alkyIsulfinyl, C1-C6alkoxycarbonyI-C1-C6alkylsulfonyl, C1~C6alkyIsulfonyIoxy, C1-C6haIoalky!sulfonyloxy, phenyl, benzyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, benzylthio, benzylsulfinyl or benzylsulfonyl, it being possible for the phenyl groups to be substituteC1 one or more times by halogen, methyl, ethyl, trifluoromethyl, methoxy or by nitro; or the group -R1-X1-R2 together is a three- to ten-membereC1, monocyclic or fuseC1 bicyclic, ring system, which may be aromatic, partially saturateC1 or saturateC1 anC1 which may contain from 1 to 4 hetero atoms selecteC1 from nitrogen, oxygen anC1 sulfur anC1/or may contain one or two groups selecteC1 from -C(=0)-, -C(=S)-, -C(=NR20)-, -(N=0)-, -S(=0)-anC1 -S02-, the ring system either being attacheC1 to the pyriC1ine ring C1irectly via a carbon atom or being attacheC1 to the pyriC1ine ring via a carbon atom or via a nitrogen atom by way of a C1-C1alkylene, C2-C4alkenyl or C2-C4alkyny! chain, anC1 it being possible for each ring system to contain no more than 2 oxygen atoms anC1 no more than two sulfur atoms, anC1 it being possible for the ring system itself to be substituteC1 one, two or three times by substituents selecteC1 from C1C1alkyl, C1C6haloalkyl, C3-C1>aIkenyl, C3-C6haloalkenyl, C3-Cealkynyl, C3-C6haloalkynyl, C3-C6cycloalkyl, hyC1roxy, C1-C1>a!koxy, C1-C6haloalkoxy, C1r C6alkenylC1xy, C3-C6alkynyloxy, mercapto, C1-C6alkylthio, C1-C1>haloa!kylthio, C3-C6alkenylthio, C3-C1>haloalkenylthio, C1-C1alkynylthio, C1-C3alkoxy-C1-C3alkylthio, C1-C3alkylcarbonyl-C1-C3alkylthio, C1-C1a!koxycarbonyI-C1-C3alkylthio, cyano-C1-C3alkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl, C1C2a!kylaminosulfonyl, C1i(C1C6alkyl)aminosulfonyl, C1-C3aIkylene-Rn6, amino, C1-Cealkylamino, C1-C6alkoxyamino, C1i(C1-C6alkyI)amino, (N-C1C6alkyI)-C-,-C6aIkoxyamino, halogen, cyano, nitro, phenyl, benzyloxy anC1 benzylthio, it being possible for phenyl, benzyloxy anC1 benzylthio to be in turn substituteC1 on the phenyl ring by C1 C3alkyl, Ct-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or by nitro, anC1 substituents on a nitrogen atom in a heterocyclic ring being other than halogen; R13 is N(H)-C1-C6alkyl, N(H)-C1C6alkoxy, N-(C1-C6alky!)-C1-C6aIkyl, N-(C1-C6alkyl)-C1-C6alkoxy, C1C6alkoxy, C1-Cehaloalkoxy, C1C6alkyl, C-,-C6haIoalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C3-C6cycloalkyl or phenyl, it being possible for phenyl to be in turn substituteC1 by C1-C3a!kyl, C1-C1haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or by nitro; R14 is N(H)-C1C6alkyl, N(H)-C1-C6alkoxy, N-CC1-CealkyO-C1CealkyI, N-(C1-C6alkyl)-C1C6alkoxy, C1C6alkoxy, C1-Cehaloalkoxy, C1-C6alkyl, C1C6haloaIkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C3-C6cycloaIkyl or phenyl, it being possible for phenyl to be in turn substituteC1 by C1-C3a!kyl, C1-C1haloalkyl, C1-C3alkoxy, C1-C3haloa!koxy, halogen, cyano or by nitro; R15 is N(H)-C1C6alkyl, N(H)-C1-C6alkoxy, N-(C1-C6a)kyl)-C1-C6alky], N-(C1-C6alkyI)-C1-C6alkoxy, C1C6alkoxy, C1-Cehaloalkoxy, C1-C6alkyl, C1-Cehaloalkyl, C1rC1>alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C3-C6cycloalkyI or phenyl, it being possible for phenyl to be in turn substituteC1 by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or by nitro; R16 is C1C3alkoxy? C2-C4alkoxycarbonyl, C1-C3a!kylthio, C1C3alkylsutfinyl, C1-C3alkyl-sulfonyi or phenyl, it being possible for phenyl to be in turn substituteC1 by C1-C3a!kyl, C1-C3haloalkyl, C1-C1alkoxy, C1-C3haloa!koxy, halogen, cyano or by nitro; anC1 R19 anC1 R20 are each inC1epenC1ently of the other hyC1rogen, hyC1roxy, C1-C6alkyI, Cn-Cehaloalkyl, C1C6alkoxy, cyano, C1Cealkylcarbonyl, C1C6alkoxycarbonyl or C1-C6alky)sulfonyl; which process comprises reacting a compounC1 of formula II wherein R3 is C1-C8alkyl or C3-C6cycloalkyl anC1 R4 anC1 R05 are as C1efineC1 for formula I, with a compounC1 of formula III wherein R, Ri, R2 anC1 X, are as C1efineC1 for formula I, in an inert solvent in the presence of a proton source. 2. A process accorC1ing to claim 1, wherein there is prepareC1 a compounC1 of formula I wherein R4 is halomethyl or haloethyl; Ros is hyC1rogen; Xt is oxygen, -O(CO)-, -(CO)O-, -O(C0)0-, -N(R6)-0, -0-NR17-, thio, sulfinyl, suifonyl, -SO2NR7-, -NR18S02- or -NR8-; R2 is hyC1rogen or C1-C1»alkyl, or a C1-C8alkyl, C3-C6alkenyl or C3-C6alkynyl group which is substituteC1 one or more times by halogen, hyC1roxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, C1-C6alkoxy, C1C1alkoxycarbonyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6- alkynyl, C2-C6haIoalkynyl, C3-C6cyC1oalkyl, halo-substituteC1 C3-C6cycloalkyl, or by C3-Cealkenyioxy, C3-C6alkynyloxy, C1-C6haloalkoxy, C3-C6haloalkenyloxy, cyano- C1C6aIkoxy, C1-Cealkoxy-C1-Cealkoxy, C1Cealkoxy-C1-Cealkoxy-C1Cealkoxy, C1-C6a!kyl- thio-C-i-Cealkoxy, C1Cealkylsulfinyl-C^Cealkoxy, C1-C6alkylsuIfonyl-C1-C6alkoxy, C1-C6- alkoxycarbonyl-C1-C6alkoxy, C1-C6alkoxycarbonyl, C1-C6alkylcarbonyl, C1Cealkylthio, C1Cealkylsulfinyl, C1-C6alkylsulfonyl, C1C6haloalkylthio, C1-C6haIoalkylsulfinyl, C1-C6- haloalkylsulfonyl, oxiranyl (which may in turn be substituteC1 by C1-C6alkyl), or by (3-oxetanyl)oxy (which may in turn be substituteC1 by C1-C6alkyl), or by benzylthio, benzylsulfinyl, benzylsulfonyl, C1-C6alkylamino, C1i(C1C6alkyI)amino, R9S(0)20-, FlioN(R1i)S02-, rhoC1ano, phenyl, phenoxy, phenylthio, phenylsulfinyl or by phenylsulfonyl; it being possible for the phenyl- or benzyl-containing groups to be in turn substituteC1 by one or more C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1C6haloalkoxy, halogen, cyano, hyC1roxy or nitro groups, or R2 is phenyl which may be substituteC1 one or more times by C1-C6alkyl, C1-C6ha!oalkyl, C1-C6a!koxy, C1-C6haloalkoxy, halogen, cyano, hyC1roxy or by nitro; or R2 is C3-C6cyc!oaIkyl, C1-C6alkoxy- or C1C6alkyl-substituteC1 C3-C6cycloaIkyl, 3-oxetanyl or C1C6alkylTsubstituteC13-oxetanyI; or R2 is a five- to ten-membereC1, monocyclic or fuseC1 bicyclic, ring system which may be aromatic, partially saturateC1 or fully saturateC1 anC1 may contain from 1 to 4 hetero atoms selecteC1 from nitrogen, oxygen, sulfur, anC1/or may contain the group -C(=0)-, -C(=S)-> -C(=NR19)-, -(N=0)-, -S(=0)» or -S02-, the ring system being attacheC1 to the substituent Xi C1irectly or by way of a C1C4alkylene, C2-C4alkenyl-C1-C4alkylene, C2-C4alkynyl-C1C4alkylene, -N(R12)-C1-C4alkylene, -SO-C1-C4alkylene or -S02-C1C4alkylene group anC1 each ring system containing no more than 2 oxygen atoms anC1 no more than two sulfur atoms, anC1 it being possible for each ring system itself to be substituteC1 one or more times by C1.-C6aIkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyi, C2-C6alkynyl, C2-C6hafoaIkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyIoxy, mercapto, amino, hyC1roxy, C1-C6alkylthio, C1-C1>haloalkylthio, C3-C6aIkenylthio, C3-C6halo-alkenylthiC1, C3*C6alkynylthio, C1-C1aIkoxy-C1C3aIkylthio, C1C4alkylcarbonyl-C1-C3alkyl-thio, C1C4alkoxycarbonyl-C1C3alkylthio, cyano-C1-C3alkylthio, C1C6alky)sulfinyl, C1C6haloalkyIsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsuIfonyI, aminosulfonyl, C1C2alkylaminosulfonyl, N,N-C1i(C1C2alkyl)aminosulfonyl, C1i(C1-C4a)kyl)amino, halogen, cyano, nitro or by phenyl, it being possible for the phenyl group to be in turn substituteC1 by hyC1roxy, C1-C6alkylthio, C1-C1>haloa!kylthio, QrCealkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C1-C1alkoxy-C1-C3alkylthio, C1-C1alkylcarbonyl-C1-C3aIky)thio, C1C1-alkoxycarbonyl-C1-C3alkylthio, cyano-C1C3alkylthio, C1C6aIkylsulfinyl, C1-C6ha!oalkyI-sulfinyl, C1-Cealkylsulfonyl, C1-C6haloalkylsuIfonyl, aminosulfonyl, C1C2alkylaminosulfony!, N,N-C1i(C1-C2a!kyl)aminosulfonyl, C1i(C1C1a(kyl)amino, halogen, cyano or by nitro, anC1 the substituents on nitrogen in a heterocyclic ring being other than halogen; Re, R7, Rs> R9, R10 R11, Ria, R17 anC1 Ri8 are each inC1epenC1ently of the others hyC1rogen, C1-C6alkyl, C1-C1shaloalkyl, C1C6alkoxycarbonyl, C1-C6alkylcarbonyl, C1C6alkoxy-C1-C6alkyl, C1C6alkoxy-C1C6alkyl substituteC1 by C1C6alkoxy, benzyl, or phenyl, it being possible for phenyl anC1 benzyl to be in turn substituteC1 one or more times by C1-C6alkyl, C1-C6haloalkyl, C1C6alkoxy, C1-C6haloalkoxy, halogen, cyano, hyC1roxy or by nitro; R6 not being hyC1rogen when R9 is hyC1rogen, C1-Cealkoxycarbonyl or C1-C6a)kyIcarbonyl; or the group -R1-X1-R2 together is C1-C1alkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6-alkynyl, C2-C6haloalkynyl, C3-C6cycloalkyl, C1C6alkoxy, C1C6haloalkoxy, C1-C6aIkylthio, C1C6alkyIsulfinyI, C1C6alkylsulfonyl, C1C6haloaIkyl, C1-C6haloatkylthio, C1-C6ha!oalkyI-sulfinyf, C1-C6haloa!kyIsuIfonyI, C1C6alkoxycarbonyl, C1-C6alkylcarbonyl, C1C6alkylamino, C1i(C1C6alky!)amino, C1-C6aIkylaminosulfonyl, C1i(C1-C6alkyI)aminosuIfonyl, -NH-S-R13, -N-(C1C4aIky!thio)-R13? -NH-SO-R14, -N-(C1-C1alkylsuIfonyI)-R14, -NH-SO2-R15, hi -N-(C1-C4alkyisulfonyl)-R15, nitro, cyano, halogen, hyC1roxy, amino, formyl, rhoC1ano-C1-C6alkylf cyano-C1-C6alkyl, oxiranyl, C3-C6alkenyloxy, C1-C6alkynyloxy, C1-C6alkoxy-C1C6a!koxy, cyano-C1-C6alkenyloxy, C1-C6alkoxycarbonyloxy-C1-C1;aikoxy, C3-C6alkynyl-oxy, cyano-C1-C1alkoxy, C1-C6alkoxycarbonyl-C1-C6aIkoxy, C1-C6alkylthio-C1-C6aIkoxy, a!koxycarbonyI-C1-C6alkylthio, alkoxycarbonyl-C1-C1>alkylsulfinyl, alkoxycarbonyl-C1-C6alkylsulfonyl, C1-C6alkylsulfonyloxy, C1-CehaloalkylsuIfonyloxy, phenyl, benzyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, benzylthio, benzylsulfinyl or benzylsulfonyl, it being possible for the phenyl groups to be substituteC1 one or more times by halogen, methyl, ethyl, trifluoromethyl, methoxy or by nitro; or the group -Ri-X1-R2 together is a five- to ten-membereC1, monocyclic or fuseC1 bicyclic, ring system, which may be aromatic or partially saturateC1 anC1 which may contain from 1 to 4 hetero atoms selecteC1 from nitrogen, oxygen anC1 sulfur, the ring system either being C1irectly attacheC1 to the pyriC1ine ring or being attacheC1 to the pyriC1ine ring by way of a C1C1alkylene group, anC1 it being possible for each ring system to contain no more than 2 oxygen atoms anC1 no more than two sulfur atoms, anC1/or to contain the group -C(=0)-, -C(=S)-, -C(=NR2oK -(N=Oh -S(=0)- or -S02-; anC1 the ring system itself may be substituteC1 one, two or three times by C1-C6alkyl, C-rQe-haloalkyl, C3-C6alkenyl, C3-C6haloaIkenyl, C1rC1alkynyl, C3-C6haloalkynyl, C1C6alkox/,;! C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, C1C6aikylthio, C1-C6- i haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C2-C5alkoxyalkyl-\| Mo, C3-C5acetylalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C1cyanoalkylthio, C1-C6alkyI-sulfinyl, C1C6haloaIkylsulfinyl, C1-C6alkylsulfonyl, (VCehaloalkylsulfonyl, aminosulfonyl, C1-C2aIkylaminosulfonyl, C2-C1C1ialkylaminosulfonyI, C1-C3alky!ene-R16, N(H)~C1-C6alkyl, N(H)-C1-C6aIkoxy, N-(C1C6alkyl)-C1-C6alkyl, N-(C1-CealkyI)-C1-C^lkoxy, halogen, cyano, nitro, phenyl anC1 by benzylthio, it being possible for phenyl anC1 benzylthio to be in turn substituteC1 on the phenyl ring by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or by nitro, anC1 substituents on nitrogen in a heterocyclic ring being other than halogen; anC1 R19 anC1 R2o are each inC1epenC1ently of the other hyC1rogen, hyC1roxy, C1-C6aIkyI, C1-C6-haloalkyl, C1-C6alkoxy, C1-C6alkylcarbonyl, C1C6alkoxycarbonyl or C1-C6aIkylsulfonyl.

Full Text

PROCESS FOR THE PRODUCTION OF SUBSTITUTED NICOTINIC ACID ESTERS
The present invention relates to a novel process for the preparation of 6-haloalkyl~3-nicotinic acid esters and also to novel enarnine intermediates for use in that process.
6-Haloalkyl-3-nicotinic acid esters are valuable intermediates for the preparation of herbicides such as those described, for example, in WO 01/94339.
From Heterocycles, Vol. 48, No. 4,1998, pages 779-785 it is known to prepare 6-trifluoro-3-nicotinic acid ethyl esters substituted by aryl in the 4-position, corresponding to formula A, by means of dehydrogenation and subsequent oxidation of the compound of formula B in accordance with the following scheme

As a result of the uneconomic multi-step procedure, that process is not well suited to the large-scale preparation of 6-haloalkyl-3-nicotinic 3cid ethyl esters.
According to Heterocycles, Vol. 46,1997, pages 129-132, 6-trifluoro-3-nicotinic acid methyl esters substituted by phenyl or alkyl in the 2-position, corresponding to formula C,

can be prepared by reacting a compound of formula E with a compound of formula D in benzene and in the presence of trifluoroacetic acid. In addition to unsatisfactory yields,
SUBSTITUTE SHEET (RULE 26)

that process has the serious disadvantage for large-scale preparation that the quality of the enamin'e (E) used as starting material continuously deteriorates during storage as a result of polymerisation reactions, making it considerably more difficult to ensure a consistent product quality.
The problem of the present invention is consequently to make available a novel process for the preparation of 6-haloalkyl-3-nicotinic acid esters which makes it possible to prepare those compounds at reasonable cost, in high yields and with good quality.
The present invention accordingly relates to a process for the preparation of compounds of formula I
wherein R is d-Cealkyl;
R05 is Hydrogen, d-C3alkyI, d-C3haloalkyl or Ci-C3alkyI-Ci-C3aIkoxy; Ri is a CrC6alkylene, C3-C6alkenylene or C3-C6alkynylene chain which may be substituted one or more times by halogen and/or by R5, the unsaturated bonds of the chain not being attached directly to the substituent Xi; R4 is CrC4haloalkyl;
X1 is oxygen, -O(CO)-, -(CO)O-, -0(CO)0-, -N(R6)-0-, -0-NR17-, thio, sulfinyl, sulfonyl, -S02NR7-, -NR18S02-, -N(S02R18a)-, -N(R18b)C(0)- or -NR8-; R18a is C1-C6alkyl;
R2 is hydrogen or C1-C8alkyI, or is a C1-C8a!kyI, C3-C6alkenyl or C3-C6alkynyl group which may be substituted one or more times by substituents selected from halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, CrC6alkoxy, d-C6alkoxycarbonyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyI, C2-C6haloalkynyI, C3-C6cycloalkyl, halo-substituted C3-C6cycloalkyl, C3-C6alkenyloxy, C3-C6alkynyloxy,C1-C6haloalkoxy, C3-C6haloalkenyloxy, cyano-C1-C6alkoxy, C1-C6aikoxy-C1-C6aIkoxy,C1-C6alkoxy-d-d>alkoxy-C1--C6alkoxy, C1-Cealkylthio-d-C6alkoxy, C1-C6alkylsulfinyl-C1-Ce-6alkoxy, d-

C6alkylsulionyl-C1-C6alkoxy, C1-C6aIkoxycarbonyl-C1-C6alkoxy, C1-C6alkylcarbonyl, C1-C6aIkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylthio, C1-C6haloalkylsulfinyl, CrC6haloalkylsulfonyI, oxiranyl (which may in turn be substituted by C1-C6alkyl), (3-oxetanyl)oxy (which may in turn be substituted by C1-C6alkyl), benzyloxy, benzylthio, benzylsultinyl, benzylsulfonyl, Ci-C6alkylamino, di(C1-C6aikyI)arnino, R9S(0)20-, R10N(R11)SO2-, rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl and phenylsulfonyl; it being possible for the phenyl- or benzyl-containing groups to be in turn substituted by one or more C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy, halogen, cyano, hydroxy or nitro groups, or
R2 is phenyl which may be substituted one or more times by C1-C6alkyI, C1-C6haloaIkyl, CrC6alkoxy, C-,-C6haloalkoxy, halogen, cyano, hydroxy or by nitro; or R2 is C3-C6cycloalkyl, d-C6alkoxy- or d-C6alkyl-substituted C3-C6cycloalkyl, 3-oxetanyl or CrC6alkyl-substituted 3-oxetanyl; or
R2 is a three- to ten-membered, monocyclic or fused bicyclic, ring system which may be aromatic, partially saturated or fully saturated and may contain from 1 to 4 hetero atoms selected from nitrogen, oxygen, sulfur, and/or may contain the group -C(=0)-, -C(=S)-, -C(=NR19)-, -(N=0)-, -S(=0)- or -S02-, the ring system being attached to the substituent X1 either directly or by way of a d-dalkylene, C2-C4alkenylene, C2-C4alkynylene, -N(R12)-CrC4alkylene, -O-d-dalkylene, -S-d-dalkylene, -SO-CrC4alkylene or -S02-Ci-C4alkylene group and each ring system containing no more than 2 oxygen atoms and no more than two sulfur atoms, and it being possible for each ring system itself to be substituted one or more times by c1-C6alkyl, C1-C6haloalkyl, C1--C6alkenyl, C2-C6halo-alkenyl, C2-C6alkynyl, C^Cehaloalkynyl, Ci-C6aIkoxy, CrC6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, amino, hydroxy, CVQealkylthio, d-d>haloalkylthio, C3-C6-alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, CrC3alkoxy-CrC3alkylthio, d-C4alkyl-carbonyl-d-C3alkylthio, CrC4alkoxycarbonyl-Ci-C3alkylthio, cyano-CrC3alkylthio, Ci-C6-alkylsulfinyl, d-C6haloaIkylsulfinyl, d-C6alkylsulfonyl, CrC6haloalkylsulfonyl, amino-sulfonyl, CrC2alkylaminosulfonyl, N,N-di(CrC2alkyI)aminosulfonyl, di(C1-C4alkyl)amino, halogen, cyano, nitro or by phenyl, it being possible for the phenyl group to be in turn sQbstituted by hydroxy, CrC6alkylthio, d-C6haloalkylthio, C3-C6alkeny!thio, C3-C6halo-alkenylthio, C3-C6alkynylthio, d-C3alkoxy-d-C3alkylthio, CT-dalkylcarbonyl-d-dalkyl-thio, C1-C4alkoxycarbonyl-d C1-alkylthio, cyano-CrC3alkylthio,C1--C6alkylsulfinyl,C1-C6-haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsuIfonyl, aminosulfonyl, C1-C2alkyl-

aminosulfonyl, N,N-C1i(C1-C2aIkyl)aminosulfonyl, C1i(C1-C4a!kyl)amino, halogen, cyano or by nitro, anC1 the substituents on nitrogen in a heterocyclic ring being other than halogen; R5 is hyC1roxy, C1-C6alkoxy, C3-C6cycloalkyloxy? C1-C6alkoxy-C1-C6alkoxy, C1-C6alkoxy-C-rC6alkoxy-C1-C6alkoxy or C1C2alky!sulfor]yloxy;
Re, R7, Rs, R9, R10 Rn, R12, Ri7, R18 anC1 R18b are each inC1epenC1ently of the others hyC1rogen, C1-C6alkyl, C1C6ha)oalkyl, C1-C6alkoxycarbonyl, C1C6alkylcarbonyl, C1-C1r alkoxy-C1-C6alkyl, C-rC6alkoxy-C1C6alkyl substituteC1 by C1-C6a!koxy, benzyl, or phenyl, it being possible for phenyl anC1 benzyl to be in turn substituteC1 one or more times by C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy, halogen, cyano, hyC1roxy or by nitro; R6 not being hyC1rogen when R9 is hyC1rogen, C1-C6alkoxycarbonyl or C1C6alkylcarbonyl;
or the group -R^X-pRa together is C1-C6alkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6-alkynyl, C2-C6haloalkynyl, C3-C6cycloalkyl, C^C1alkoxy, C1C6haloalkoxy, C1-C6alkylthio, C1-C6alky)sulfinyl, C1-C6alkyIsulfonyl, C1-C6haloalkyl, C1-C6haloalkylthio, C1-C1haloalkyl-sulfinyl, C1-C1shaloalkylsulfonyl, C1C6alkoxycarbonyl, C1-C1alkylcarbonyl, C1-C6alkylamino, C1i(C1-C6alkyl)amino, C1-C6alkylaminosutfonyl, C1i(C1~C6alkyl)aminosulfonyl, -NH-S-R13, -N-(C1C4aIkylthio)-Ri3, -NH-SO-R14, -N-(C1-C1alkylsulfonyl)-R14, -NH-SO2-R15, -N-(C1-C1alkyIsulfonyI)-R15, nitro, cyano, halogen, hyC1roxy, amino, formyl, rhoC1ano-C1-C6-alkyl, cyano-C1-C6alkyl, oxiranyl, C3-C6alkenyloxy, C3-C6aIkynyloxy, C1-C6alkoxy-C1-C6-alkoxy, cyano-C1-C6alkenyloxy, C1-C6alkoxycarbonyioxy-C1C1alkoxy, C3-C6alkynyloxy, cyano-C1-C6a!koxy, C1C6alkoxycarbonyl-C1-C6alkoxy, C1-C6alkylthio-C1-C1alkoxy, C1-C6alkoxycarbonyl-C-1-C6alkylthio, C1C6alkoxycarbonyl-C1-C6alkylsulfinyl, C1-C6alkoxycarbonyl-C1-C6alkylsulfonyLC1-C6alkylsulfonyloxy, C1-C6haloalkyIsulfonyloxy, phenyl, benzyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, benzylthio, benzylsulfinyl or benzylsulfonyl, it being possible for the phenyl groups to be substituteC1 one or more times by halogen, methyl, ethyl, trifluoromethyl, methoxy or by nitro; or the group -R1-X1-R2 together is a three- to ten-membereC1, monocyclic or fuseC1 bicyclic, ring system, which may be aromatic, partially saturateC1 or saturateC1 anC1 which may contain from 1 to 4 hetero atoms selecteC1 from nitrogen, oxygen anC1 sulfur anC1/or may contain one or two groups selecteC1 from -C(=0)-, -C(=S)-, -C(=NR20)-, -(N=0)-, -S(=0)-anC1 -S02-; the ring system either being attacheC1 to the pyriC1ine ring C1irectly via a carbon atom or being attacheC1 to the pyriC1ine ring via a carbon atom or via a nitrogen atom by way of a C1-C4alkylene, C2-C4alkenyl or C2-C4alkynyl chain, anC1 it being possible for each ring system to contain no more than 2 oxygen atoms anC1 no more than two sulfur atoms,

anC1 it being possible for the ring, system itself to be substituteC1 one, two or three times by substituents selecteC1 from C1-C6alkyl, C1-C6haloaIkyI, C3-C6alkenyl, C3-C6haloa!kenyI, C3-C6alkynyl, C3-C6haloalkynyK C3-C6cycloaIkyl, hyC1roxy, C1-C6alkoxy, C1C6haloalkoxy, C3-C6alkenyloxy, C3-C6aIkynyloxy, mercapto, C1-C6alkylthio, C1-C6haIoalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynyIthio, C1-C1alkoxy-C1-C1alkylthio, C1-C3alkylcarbonyl-C1-C3aIkylthio, C1-C1alkoxycarbonyl-C1C1alkylthio, cyano-C1-C1alkylthio, C1C6aIkylsuIfinyl, C1-C1haloalkylsulfinyl, C1C6alkylsulfonyl, C1C6haloaIkylsulfonyl, aminosulfonyl, C1-C2aIkyIaminosulfonyl, C1i(C1C6alkyl)aminosulfonyl, C1-C3alkylene-R16, amino, C1-C6alkylamino, C1-C6alkoxyarnino, C1i(C1C6alky!)amino, (N-C1-C6alkyI)-C1-C6aIkoxyamino, halogen, cyano, nitro, phenyl, benzyloxy anC1 benzylthio, it being possible for phenyl, benzyloxy anC1 benzylthio to be in turn substituteC1 on the phenyl ring by C1 C3alkyl, C1-C3haloalkyl, C1-C1alkoxy, C1C3haloalkoxy, halogen, cyano or by nitro, anC1 substituents on a nitrogen atom in a heterocyclic ring being other than halogen; R13 is N(H)-C1-C6aIkyi, N(H)-C1C6alkoxy, ISKC1-C6a[kyl)-C1-C6aIkyI, N-(C1-C6alky()-C1-C6alkoxy, C1-C6alkoxy, C1-C6haloalkoxy, C1-C1>alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C3-C6cycloalkyl or phenyl, it being possible for phenyl to be in turn substituteC1 by C1-C3alkyl, C1C3haloalkyI, C1-C3alkoxy, C-i-Cshaloalkoxy, halogen, cyano or by nitro;
R14 is N(H)-C1-C6alkyl, N(H)-C1C6alkoxy, N-(C1-C6aIkyI)-C1-C6alkyl, N-(C1-C6aIky!)-C1-C6alkoxy, C1-C1>a!koxy, C1-C6haloalkoxy, C1C6alkyl, C1-C6haloalkyl, C1-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C3-C6cycloalkyl or phenyl, it being possible for phenyl to be in turn substituteC1 by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1C3haloalkoxy, halogen, cyano or by nitro;
R15 is N(H)-C1-C6alkyl, N(H)-C1-C6alkoxy, N-(C1C6alkyl)-C1C6alkyl, N-(C1-C6alkyi)-C1-C6alkoxy, C1-C6a)koxy, C1C6haloalkoxy, C1-C6alkyl, C1C6haloalkyl, C3-C6alkenyl, C3-C6haloalkenylr C3-C6alkynyl, C3-C6haloalkynyl, C1-C6cycloalkyl or phenyl, it being possible for phenyl to be in turn substituteC1 by C1-C1alkyl, C1-C3haloalkyl, C1-C1alkoxy, C1-C3haloalkoxy, halogen, cyano or by nitro;
R16 is C1-C3alkoxy, C2-G4a!koxycarbonyl, C1C3alkylthio, C1C1alkylsulfinyl, C1-C3alkyl-stilfonyl or phenyl, it being possible for phenyl to be in turn substituteC1 by C1-C3a!kyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or by nitro; anC1 Rt9 anC1 R2o are each inC1epenC1ently of the other hyC1rogen, hyC1roxy, C1-C6a!kyl, C1-C6haloalkyl, C1-C6alkoxy, cyano, C1-C6a!kylcarbonyI, C1-C6aIkoxycarbonyl or C1-C6alkylsulfonyl; which proC6ss comprises reacting

a compounC1 of formula II

wherein R3 is C1-C8alkyl or C3-C6cycloalkyl anC1 R4 anC1 R05 are as C1efineC1 for formula I, with a compounC1 of formula III

wherein R, R17 R2 anC1 X-j are as C1efineC1 for formula I, in an inert solvent in the presenC6 ol a proton sourC6.
The alkyl groups appearing in the substituent C1efinitions may be straight-chaineC1 or brancheC1 anC1 are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl anC1 octyl anC1 also the brancheC1 isomers thereof. Alkoxy, alkenyl anC1 alkynyl groups are C1eriveC1 from the mentioneC1 alkyl groups. The alkenyl anC1 alkynyl groups may be mono- or poly-unsaturateC1.
Halogen is generally fluorine, chlorine, bromine or ioC1ine, preferably fluorine or chlorine. The same is also corresponC1ingly true for halogen in conjunction with other meanings such as haloalkyl or halophenyl.
Haloalkyl groups preferably have a chain length of from 1 to 6 carbon atoms. Haloalkyl is, for example, fluoromethyl, C1ifluoromethyl, trifluoromethyl, chloromethyl, C1ichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-C1ifluoro-2r2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl or 2,2,2-trichloroethyl; preferably trichloromethyl, C1ifluorochloromethyl, C1ifluoromethyl, trifluoromethyl or C1ichlorofluoro-methyl.

As haloalkenv! there come into consiC1eration alkenyl groups substituteC1 one or more times by halogen, halogen being fluorine, chlorine, bromine or ioC1ine, espeC1ally fluorine or chlorine, for example 2,2-C1ifluoro-1-methylvinyl, 3-fluoropropenyl, 3-chloropropenyi, 3-bromopropenyl, 2,3,3-trifluoropropenyl, 2,3,3-trichloropropenyl anC1 4,4,4-trifluoro-but-2-en-1-yl. Among the C3-C6alkenyl groups substituteC1 onC6, twiC6 or three times by halogen, preferenC6 is given to those that have a chain length of from 3 to 5 carbon atoms.
As haloalkynyl there come into consiC1eration alkynyl groups substituteC1 one or more times by halogen, halogen being bromine, ioC1ine or, espeC1ally, fluorine or chlorine, for example 3-fluoropropynyl, 3-chloropropynyl, 3-bromopropynyl, 3,3,3-trifluoropropynyl anC1 4,4,4-trifluoro-but-2-yn-1-yl. Among the alkynyl groups substituteC1 one or more times by halogen, preferenC6 is given to those that have a chain length of from 3 to 5 carbon atoms.
Alkoxy groups preferably have a chain length of from 1 to 6 carbon atoms. Alkoxy is, for example, methoxy, etboxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy or tert-butoxy or the pentyfoxy or hexyloxy isomers; preferably methoxy or ethoxy. Alkylcarbonyl preferably is aC6tyl or propionyl. Alkoxycarbonyl is, for example, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxy-carbonyl, sec-butoxycarbonyl or tert-butoxycarbonyl; preferably methoxycarbonyl or ethoxycarbonyl. Haloalkoxy groups preferably have a chain length of from 1 to 8 carbon atoms. Haloalkoxy is, for example, fluoromethoxy, C1ifluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-C1ifluoroethoxy or 2,2,2-trichloroetboxy; preferably C1ifluoromethoxy, 2-chlorethoxy or trifluoromethoxy. Alkylthio groups preferably have a chain length of from 1 to 8 carbon atoms. Alkylthio is, for example, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio or tert-butylthio, preferably methylthio or ethylthio. Alkylsulfinyl is, for example, methylsulfinyl, ethylsulfinyl, propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec~buty!suifinyl or tert-butylsulfinyl; preferably methylsulfinyl or ethylsulfinyl.
Alkylsulfonyl is, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropyl-sulfonyl, n-butylsulfonyl, isobutylsylfonyl, sec-butylsulfonyl ortert-C1utylsulfonyl; preferably

methylsulfonyl or ethylsulfonyi. Alkoxyalkoxy groups preferably have a chain length of from 1 to 8„ carbon atoms. Examples of alkoxyalkoxy are: methoxymethoxy, methoxyethoxy, methoxypropoxy, ethoxyrnethoxy, ethoxyethoxy, propoxymethoxy anC1 butoxybutoxy. Alkylamino is, for example, rnethylamino, ethylamino, n-propylamino, isopropylamino or the butylamine isomers. C1ialkylamino is, for example, C1imethylamino, methylethylamino, C1iethylamino, n-propylmethylamino, C1ibutylamino or C1iisopropylamino. PreferenC6 is given to alkylamino groups having a chain length of from 1 to 4 carbon atoms. Alkoxyalkyl groups preferably have a chain length of from 2 to 6 carbon atoms. Alkoxyalkyl is, for example, methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethy), n-propoxymethyl, n-propoxyethyl, isopropoxymethyl or isopropoxyethyl. Alkylthioalkyl groups preferably have from 2 to 8 carbon atoms. Alkylthioalkyl is, for example, methyl-thiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, n-propylthiomethyl, n-propyl-thioethyl, isopropylthiomethyl, isopropylthioethyl, butylthiomethyl, butylthioethyl or butylthiobutyl. The cycloalkyl groups preferably, have from 3 to 8 ring carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl anC1 cyclooctyl. Phenyl, incluC1ing phenyl as part of a substituent such as phenoxy, benzyl, benzyloxy, benzoyl, phenylthio, phenylalkyl anC1 phenoxyalkyl, may be present in substituteC1 form, in which case the substituents may be in the ortho-, meta- anC1/or para-position(s). PreferreC1 substituent positions are the positions ortho anC1 para to the ring attachment position.
In accorC1anC6 with the proC6ss accorC1ing to the invention there are preferably prepareC1
those compounC1s of formula I wherein
R4 is halomethyl or haloethyl;
Ros is hyC1rogen;
X, is oxygen, -O(CO)-, -(00)0, -0(C0)0-, -N(R6)-0-, -0-NR17-, thio, sulfinyl, sulfonyl,
-S02NR7-, -NR18S02- or -NR8-;
R2 is hyC1rogen or C1-C6alky), or a C1C6aikyl, C3-C6alkenyl or C3-C6alkynyi group which is substituteC1 one or more times by halogen, hyC1roxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, C1-C6alkoxy, C1-C6alkoxycarbonyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6-alkynyl, C2-C6ha)oalkynyl, C3-C6cycloaIkyl, halo-substituteC1 C3-C6cycloaikyl, or by C3-C6alkenyloxy, C3-C6alkynyloxy, C1-C6haloalkoxy, C3-C6haloaIkenyloxy, cyano-C1C6aIkoxy, C1-C6aikoxy-C1C6alkoxy, C1C6alkoxy-C1C6alkoxy-C1C6alkoxy, C-i-C6alkyl-thio-C1-C6alkoxy, C1-C6alkylsuIfinyl-C1C6alkoxy, C1-C6alkylsulfonyl-C1-C6alkoxy, Ct-C6-alkoxycarbonyl-C1-C6alkoxy, C1-C6alkoxycarbonyl, C1-C6alkylcarbonyl, C1-C6alkylthio,

C1C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylthio, C1C6haloalkylsulfinyl, C1C6-haloalkylsujfonyl, oxiranyl (which may in turn be substituteC1 by C-rC6alkyI), or by (S-oxetanyl)oxy (which may in turn be substituteC1 by Cn-C6alkyl), or by benzylthio, benzylsulfinyi, benzylsulfonyl, C1-C$alkylamino, C1i(C-i-C6alkyl)amino, R9S(0)20-, RioN(Rn)S02-, rhoC1ano, phenyl, phenoxy, phenylthio, phenylsulfiny! or by phenylsulfonyl; it being possible for the phenyl- or benzyl-containing groups to be in turn substituteC1 by one or more C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy, halogen, cyano, hyC1roxy or nitro groups, or
R2 is phenyl which may be substituteC1 one or more times by C1C6alkyl, C1C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy, halogen, cyano, hyC1roxy or by nitro; or R2 is C3-C6cycloalkyl, C1C6alkoxy- or C1-C6alkyl-substituteC1 C3-C6cycloalkyl, 3-oxetanyl or C1C6alkyl-substituteC1 3-oxetanyl;
or R2 is a five- to ten-membereC1, monocyclic or fuseC1 bicyclic, ring system which may be aromatic, partially saturateC1 or fully saturateC1 anC1 may contain from 1 to 4 hetero atoms selecteC1 from nitrogen, oxygen, sulfur, anC1/or may contain the group -C(=0)-, -C(=S)-, -C(=NR19)-, -(N=0)-, -S(=0)- or -S02-, the ring system being attacheC1 to the substituent Xi C1irectly or by way of a C1-C1alkylene, C2-C4alkenyl-C1-C4alkylene, C2-C4alkynyl-C1-C4alkylene, -N(R-i2)-C1-C4aIkylene, -SO-C1C4alkylene or -S02~C1-C4alkylene group anC1 each ring system containing no more than 2 oxygen atoms anC1 no more than two sulfur atoms, anC1 it being possible for each ring system itself to be substituteC1 one or more times by C1-C6alkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C1-C6a!koxy, C1-C6haloa!koxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, amino, hyC1roxy, C1C6alkylthio, C1-C6haloalkylthio, C3-C6alkenylthio, C3-C6halo-alkenylthio, C3-C6alkynylthio, C1-C3alkoxy-C1-C3alkylthio, C1-C4alkylcarbonyl-C1-C3aIkyl-thio, C1-C4alkoxycarbonyl-C1C3alkylthio, cyano-C1-C3alkylthio, C1C6alkylsulfinyl, C1C6haloalkylsulfinyl, C1-C6alky!sulfonyI, C1C6haloaIkylsulfonyl, aminosulfonyl, C1C2alkylaminosulfonyI, N)N-C1i(C1-C2alkyl)aminosulfonyl, C1i(C1C4alkyl)amino, halogen, cyano, nitro or by phenyl, it being possible for the phenyl group to be in turn substituteC1 by hyC1roxy, C-,-C6alkylthio, C1C6haloalkylthio, C3-C6alkenylthio, C1C6haloalkenyithio, CVC6alkynyIthio, C1C3alkoxy-C1»C3alkylthio, C1C4aIkyIcarbonyI-C1C3alkylthio, C1-C1-alkoxycarbonyl-C1C3alkylthio, cyano-C1-C3alkylthio, C1-C1>alkylsulfinyl, C1C6haloalkyl-suifinyi, C1C6alkylsulfonyl, C1-G6haIoaIkyIsulfonyl, aminosulfonyl, C1C2alkyIaminosulfonyl, N,N-C1i(C1C2alkyl)aminosuIfonyl, di(C1-C4alky!)amino, halogen, cyano or by nitro, anC1 the substituents on nitrogen in a heterocyclic ring being other than halogen;

R6) R7, R8, R9, R10 R11, R12, R17 anC1 R18 are each inC1epenC1ently of the others hyC1rogen, C1C1aIkyl,C1-C6haloalkyl, C1-C6alkoxycarbonyl, C1-C6alkylcarbonyl, C1-C6a!koxy-C1C6aIkyl, C1-C6alkoxy-C1-C6alkyl substituteC1 by C-rC6aIkoxy, benzyl, or phenyl, it being possible for phenyl anC1 benzyl to be in turn substituteC1 one or more times by C1-C6alkyl, C1-C6haloalkyl, C1C6alkoxy, C1-C6haloalkoxy, halogen, cyano, hyC1roxy or by nitro; R6 not being hyC1rogen when R9 is hyC1rogen, C1-C6alkoxycarbonyl or C1C6alkylcarbonyl; or the group -R-rX^Rg together is C1C6alkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6-alkynyl, C2-C6haloaIkynyl, C3-C6cycloaIkyI, C1-C1alkoxy, C1-C6haloalkoxy, C1C6alkylthio, C1-C6alkyIsu!finyl, C1-C6alkylsulfonyl, C1-C6haloalkyl, C1-C6haloalkylthio, C1-C6haloalkyl-sulfinyl, C1C6haloalkylsulfonyl, C1-C6alkoxycarbonyl, C1-C6alkylcarbonyl, C1-C6alkylamino, C1i(C1C6alkyl)amino, C1-C6alkylaminosulfonyl, C1i(C1-C6alkyI)aminosulfonyl, -NH-S-R13, -N-(C1-C1alkyithio)-R13, -NH-SO-R14, -N-(C1C1alkylsulfonyl)-R14, -NH-S02-R15, -N-(C1-C1alkyIsulfonyl)-R15, nitro, cyano, halogen, hyC1roxy, amino, formyl, rhoC1ano-C1-C6aIkyl;cyano-C1-C6alkyl, oxiranyl, C3-C6alkenyloxy, C1-C6alkynyloxy, C1-C6alkoxy-C1-C1alkoxy, cyano-C1-C6alkenyloxy, C1-C6alkoxycarbonyloxy-C1-C6alkoxy, C1-C6alkynyI-oxy, cyano-C1-C6aIkoxy, C1-C6alkoxycarbonyl-C1-C6alkoxy, C1-C6alkylthio-C1-C6alkoxy, alkoxycarbonyl-C1C6alkylthio, alkoxycarbonyl-C1C6alkylsulfinyl, alkoxycarbonyl-C1-C6alkylsuIfonyl, C1-C6alkylsulfonyloxy, C1-C6haloalkylsulfonyloxy, phenyl, benzyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, benzylthio, benzylsulfinyl or benzylsulfonyl, it being possible for the phenyl groups to be substituteC1 one or more times by halogen, methyl, ethyl, trifluoromethyl, methoxy or by nitro;
or the group -R1-X-R2 together is a five- to ten-membereC1, monocyclic or fuseC1 bicyclic, ring system, which may be aromatic or partially saturateC1 anC1 which may contain from 1 to 4 hetero atoms selecteC1 from nitrogen, oxygen anC1 sulfur, the ring system either being C1irectly attacheC1 to the pyriC1ine ring or being attacheC1 to the pyriC1ine ring by way of a C1C1alkylene group, anC1 it being possible for each ring system to contain no more than 2 oxygen atoms anC1 no more than two sulfur atoms, anC1/or to contain the group -C(=0)-, -C(=S)-, -C(=NR2o)-, -(N=0)-, -S(=0)- or -S02-;
anC1 the ring system itself may be substituteC1 one, two or three times by C1-C6alkyl, C1-C6-haloalkyl, C3-C6alkenyl, C3-C6haloaIkenyl, C3-C6alkynylf C3-C6haloalkynyl, C1C6alkoxy, C1-C6ha!oa!koxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, C1-C6alkyIthio, C1-C6-haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C2-C5alkoxyalkyl-thio, C1-C5aC6tylalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C1cyanoalkylthio, C1-C6a!kyl-sulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl, aminosulfonyl,

C1-C2alkylaminosulfonyl, C2-C4C1ialkyIaminosuIfonyi, C1C3alkylene-R16, N(H)-C1-C6aIkyI, N(H)-C1-C6alkoxy, N-(C1-C6aikyl)-C1-C6alkyl, N-(C1-C6alkyI)-C1-C6alkoxy, halogen, cyano, nitro, phenyl anC1 by benzylthio, it being possible for phenyl anC1 benzylthio to be in turn substituteC1 on the phenyl ring by C1-C1?alkyl> C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or by nitro, anC1 substituents on nitrogen in a heterocyclic ring being other than halogen; anC1
R19 anC1 R20 are each inC1epenC1ently of the other hyC1rogen, hyC1roxy, C1-C6alkyl, C1-C6-haloalkyl, C1-C6alkoxy, C1-C6alkylcarbonyl, C1-C6alkoxycarbonyl or C1-C6alkylsulfonyl.
The proC6ss accorC1ing to the invention is espeC1ally suitable for the preparation of those compounC1s of formula I wherein Ri is -CH2-, -CH2CH2-, -CH2CH2CH2-, -CF2-, -CH=CHCHr, -CH(CH3)- or -OCCH2-, but preferably -CH2-, the free valency on the left in each case being attacheC1 to the pyriC1ine ring.
PreferenC6 is furthermore given to the preparation of those compounC1s of formula I wherein X1 is oxygen, sulfonyl or a group -NR18S02-, espeC1ally oxygen.
In accorC1anC6 with the proC6ss accorC1ing to the invention, speC1al preferenC6 is given to the preparation of those compounC1s of formula I wherein R2 is CH3, CH2CH3, CH2OCH3, CH2OCH2CH3, CH2CH2OCH3, CH2CH2OCH2CH3, CH2CF3, propargyl, cyclopropylmethyl, benzyl, CH2CH2S02CH3 or CH2CH2OCH2CH2OCH3, but preferably CH2CH2OCH3, with very speC1al preferenC6 being given to those compounC1s wherein Xi is oxygen anC1 R-, is -CHr.
In accorC1anC6 with the proC6ss accorC1ing to the invention, preferenC6 is given to the preparation of those compounC1s of formula I wherein R05 is hyC1rogen, CH3, CH2C1, CH2Br or CH2OCH3) but espeC1ally hyC1rogen.
From that group, those compounC1s wherein R is ethoxy or methoxy may be prepareC1 espeC1ally aC1vantageously.
Furthermore, in accorC1anC6 with the proC6ss accorC1ing to the invention there may be aC1vantageously prepareC1 compounC1s of formula I wherein R2 is

inC1icateC1 ip those preferreC1 meanings of R2, as in the case of, for example, ° , the attachment position is at the carbon atom markeC1 "CHFurthermore, there may also be aC1vantageously prepareC1 those compounC1s wherein the group -FVX1-R2 together is a four- to ten-rnembereC1, monocyclic or fuseC1 tricyclic, ring system, which may be aromatic, partially saturateC1 or saturateC1 anC1 contains from 1 to 4 hetero atoms selecteC1 from nitrogen, oxygen anC1 sulfur anC1/or contains one or two groups selecteC1 from -C(=0)-, -C(=S)-, -C(=NR2o)- anC1 -S02-, the ring system being attacheC1 to the pyriC1ine ring via a carbon atom or preferably via a nitrogen atom by way of a C1-C4alkylene chain, espeC1ally a methylene chain. Among such ring systems speC1al mention may be maC1e of the following preferreC1, four- to seven-membereC1 ring systems attacheC1 via a nitrogen atom to the methylene group, the attachment position being shown in each case at the bottom left:

wherein r is 0, 1 or 2; R51l R53, R56 anC1 R65 are each inC1epenC1ently of the others hyC1rogen, halogen, C1-C6alkyl, C1-C6haloalkyl, C3-C6cycloalkyl, C3-C6alkenyl, C3-C6alkynyl, C1-C3alkoxy-C1-C3aIkyl, C1-C1alkoxy, C3-C6alkenyloxy, C3-C6aIkynyloxy, C1C6alkylthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C3-C6aIkenyIthio or C3-C6aIkynylthio; R52 is hyC1rogen, C1-C6alkyI, C1-C6haloalkyl, C3-C6cycloalkyi, C3-C6alkenyl, C3-C6alkynyl, C1-C6aIkoxy, amino, or phenyl which may in turn be substituteC1 by R70; R54, R55 anC1 R60 are each inC1epenC1ently of the others hyC1rogen, C1-C6alkyl, C1-C6haloalkyl, C3-C6alkenyl, C3-C6alkynyl or C3-C6cycloalkyI; R57, R63, Res, R67, Res anC1 R69 are each inC1epenC1ently of the others C1-C6alkyI, or phenyl which may in turn be substituteC1 by R70; Re4 is C1C6alkyl, C1-C6haloalkyl, C3"C6cycloalkyl, C3-C6alkenyl, C3-C6alkynyl, or phenyl which may in turn be substituteC1 by R7o; R58 anC1 R61 are hyC1rogen, halogen, C1-C6alkyl or C^C6haloalkyl; R59 is C1-C6alkyl, C1-C6haloalkyl, C1-C3a!koxy-C1-C3alkyl, C3-C6alkenyl or C3-C6alkynyi; R62 is hyC1rogen, C1-C6alkyl, C1-C1alkoxycarbonyl or C1-C4alkylthiocarbonyI; or R51 together with Rs2, or R54 together with an aC1jaC6nt group R56, or R58 together with an aC1jaC6nt group R59, or R60 together with an aC1jaC6nt group R61, or, when r is 2, two aC1jaC6nt groups R56 or two aC1jaC6nt groups R61 together may form a saturateC1 or unsaturateC1 C1-C5aIkylene or C3-C4alkenylene briC1ge, which may in turn be substituteC1 by a group R70 or interrupteC1 by

oxygen, sulfur or nitrogen; each R7o is inC1epenC1ently halogen, C1-C3alkyl, CVCahaloalkyl, hyC1roxy, C1C3alkoxy, C1-C3haloalkoxy, cyano or nitro; X is oxygen, sulfur or NR6; X3, X4 anC1 X5 are oxygen or sulfur; X6 anC1 X7 are oxygen, sulfur, S(O) or S02; anC1 X8 is CH2, oxygen, sulfur, S(O), S02 or MR71, wherein R71 is hyC1rogen or C1-C6alkyl.
In the context of the present invention, preferenC6 is given to the group R^X^Ra together being C1C6alkyl, C1-C6haloaIkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6halo-alkynyl, C3-C6cycloalkyl, C1C6alkoxy or C1-C6alkylthio, e.g. methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, fluoromethyl, 2-fluoroethyl, C1ifluoroethyl, trifluoroethyl, vinyl, i-propenyl, methoxy, ethoxy, methylthio or ethylthio.
In the context of the present invention, preferenC6 is given to R being methyl, ethyl, n-propyl or isopropyl, espeC1ally ethyl.
R3 is preferably methyl or ethyl, very espeC1ally ethyl.
R4 is preferably trifluoromethyl, C1ifluoromethyl, chloroC1ifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, espeC1ally trifluoromethyl, chloroC1ifluoromethyl or C1ifluoromethyl.
As inert solvents for the methoC1 accorC1ing to the invention there are suitable, for example, aromatic solvents such as benzene, chlorobenzene, fluorobenzene, xylenes, toluene, or alcohols such as methanol or ethanol, anC1 also ethyl aC6tate, aC6tonitrile, C1imethyl sulfoxiC1e, C1imethylformamiC1e, C1imethylaC6tamiC1e, N-methyl-2-pyrroliC1one, aC6tone, butanone, halogenateC1 solvents such as, for example, methylene chloriC1e, trichloro-methane, C1ichloroethylene or trichlorethane, ethers such as tetrahyC1rofuran, C1iethyl ether, 1,2-C1imethoxyethane, C1ioxane or methyl tert-butyl ether. Ethanol anC1 toluene are espeC1ally preferreC1.
Organic or mineral aC1C1s are suitable as the proton sourC6. Examples of suitable proton sourC6s are HC1, HBr, H2S04, carboxylic aC1C1s such as aC6tic aC1C1 anC1 C1erivatives thereof such as trifluoroaC6tic aC1C1 anC1 trichloroaC6tic aC1C1, sulfonic aC1C1s such as methane-sulfonic aC1C1 or p-toluenesulfonic aC1C1 anC1 also carbonic aC1C1. As the proton sourC6 for the proC6ss accorC1ing to the invention speC1al preferenC6 is given to trifluoroaC6tic aC1C1.

The reactions can be carrieC1 out at ambient temperature or at elevateC1 temperature. In general, aC1C1ition of the reactants is carrieC1 out at a temperature from ambient temperature to the boiling point of the solvent, espeC1ally from 20 to 140°C, preferably from 40 to 120°C, with subsequent heating of the reaction mixture, aC1vantageously to the boiling point of the solvent.
The compounC1s of formula II are known or are acC6ssible by known methoC1s. ProC6sses for the preparation of compounC1s of formula II are C1esC1ibeC1, for example, in J. Org Chern. (1995) vol 95, 3523, in H. Amil, T. Kobayashi, H. Terasawa, K. Uneyama, Org. Lett. 3(20), 3103-3105 (2001) anC1 also A. Colla, G. Clar, S. Krimmer, P. Fischer, M.A.P. Martins, Synthesis-Stuttgart (6),483-486 (1991).
Some of the compounC1s of formula III are known. The preparation of such compounC1s is C1esC1ibeC1 in H. G. O. Becker, J. Prakt. Chem. (1961), Vol 12, 294., in WO 00/24714 anC1 also in C1.H. Wu, W. Wang, J. LabelleC1 CompC1. RaC1 39(2),105-107(1997).
The compounC1s of formula III wherein -FVX1-R2 is -CH2-0-CH2-CH2-0-CH3, that is to say compounC1s of formula Ilia

wherein R is as C1efineC1 for formula 111, are novel anC1 were C1evelopeC1 speC1fically for the preparation of compounC1s of formula I, anC1 the present invention accorC1ingly relates thereto. In a preferreC1 compounC1 of formula Ilia, R is methyl or ethyl.
CompounC1s of formula III can be prepareC1 using proC6sses known to the person skilleC1 in the art, for example by reacting the unsaturateC1 ketones on which they are baseC1 with ammonia gas as C1esC1ibeC1 in Preparation Example P1 hereinbelow.
In a preferreC1 emboC1iment of the proC6ss accorC1ing to the invention, the starting compounC1s of formula III are prepareC1 from the 3-oxo-carboxyIic aC1C1 esters on which they are baseC1 by introC1uC1ng ammonia gas anC1 then, without further isolation, reacting

C1irectly with the compounC1s of formula II. That proC6ss is espeC1ally aC1vantageous for the
large-scale preparation of compounC1s of formula I.
in
The compounC1s of formula I either may be useC1 C1irectly in the reaction mixture for further reactions or alternatively may be isolateC1. Isolation of the compounC1s of formula I can be carrieC1 out, for example, by extraction of the reaction mixture anC1 subsequent removal of the solvent from the proC1uct-containing phase by customary methoC1s.
The proC6ss accorC1ing to the invention will be explaineC1 in greater C1etail in the following Preparation Examples:
Example Pi: Preparation of 3-amino-4-methoxvethoxv-but-2-enoic aC1C1 ethyl ester:

A mixture of 1.37 g (6 mmol) of 3-oxo-4-methoxyethoxy-butanoic aC1C1 ethyl ester (1) in 13 ml of ethanol is introC1uC6C1 into a reaction vessel anC1 cooleC1 to a temperature of 0°C using an iC6/water bath.
Ammonia gas is then introC1uC6C1 for a perioC1 of 30 minutes, with stirring, anC1 the reaction mixture is stirreC1 for a further 20 minutes at a temperature of 0°C. After removing the cooling bath, the reaction mixture is alloweC1 to warm up to a temperature of 20°C anC1 ammonia gas is then introC1uC6C1 for a further hour. The reaction mixture is then stirreC1 for 20 hours.
After removal of the solvent in vacuo, there are obtaineC1 1.3 g (95 % of theory) of 3-amino-4-methoxyethoxy-but-2-enoic aC1C1 ethyl ester (2) in the form of an orange-coloureC1 oil.
1H NMR (CC1Cl3): 1.30 (t, 3H, CH3CH20-), 3.40 (s, 3H, CH30-), 3.55 (m, 2H, OCHsCHsO), 3.60 (m, 2H, OCH2CH2O), 4.10 (s, 2H, C=CC1i>0-), 4.15 (q, 2H, CH3Ch2O-), 4.50 (s, 1H, CH=CNH2).

13C NMR (CC1C13): 14.7 (CH3), 58.9 (CH2), 59.2 (CH3), 70.0 (CH2), 71.0 (CH2), 71.8 (CH2), 81.9 (CH),,159.7 (C), 170.3 (C) .
MS: 203 (M+), 158, 157, 144,129, 114, 100, 98, 83, 71, 59, 45.
Example P2: Preparation of 2-methoxvethoxvmethyl-3--ethoxvcarbonvl-6-trifluoromethvl-pyriC1ine (4):

A mixture of 52.3 g (0.24 mol) of 3-oxo-4-methoxyethoxy-butanoic aC1C1 ethyl ester (1) in 150 ml of toluene is introC1uC6C1 into a reaction vessel equippeC1 with a water separator.
Ammonia gas is then introC1uC6C1 into the reaction mixture for 2 hours, with stirring. Refluxing is then carrieC1 out for 30 minutes anC1 the water is collecteC1 in the separator. After cooling the reaction mixture to a temperature of 20°C, the proC6C1ure is repeateC1. Ammonia gas is again introC1uC6C1 for 1.5 hours, with stirring, anC1 the reaction mixture is then refluxeC1 in orC1er to separate off the water.
After cooling the reaction mixture, which contains 3-amino-4-methoxyethoxy-but-2-enoic aC1C1 ethyl ester (2), to a temperature of 20°C, 48 g (0.248 mol) of 1 -ethoxy-3-oxo-4-tnfliiorobutene (3) are aC1C1eC1 anC1 stirring is carrieC1 out at a temperature of 20°C for 18 hours. 1.5 ml of trifluoroaC6tic aC1C1 are then aC1C1eC1, stirring is carrieC1 out at a temperature of 20°C for 2 hours anC1 refluxing is carrieC1 out for a further 2 hours.
The reaction mixture is then alloweC1 to cool C1own to a temperature of 20°C anC1 is then washeC1 with 100 ml of 1M NaHC03. The aqueous phase is separateC1 off anC1 is then

extracteC1 with 150 ml of toluene anC1 the combineC1 organic phases are then C1rieC1 over
MgS04.
After removal of the solvent in vacuo, there are obtaineC1 65.4 g (62 % of theory) of 2-methoxyethoxymethyl-3-ethoxyGarbonyl-64rifluoromethylpyriC1ine in the form of a C1ark-brown oil.
'H NMR (CC1C13): 1.40 (t, 3H, CH3CH2O-), 3.35 (s, 3H, CH3O-), 3.55 (m, 2H, OCH2CH2O), 3.70 (m, 2H, OCH2CH2O), 4.45 (q, 2H, CH3CH2O-), 5.00 (s, 2H, ArCH2O-), 7.70 (s, 1H, ArH), 8.30 (s,1H, ArH).
MS: 307 (M+), 262, 248, 233, 204, 202,161, 128, 109, 59, 45
The other compounC1s listeC1 in Table 1 can also be prepareC1 in that manner.
In the following Table, the valency on the left of the raC1ical F^ is attacheC1 to the pyriC1ine ring. When no free valency is inC1icateC1 in the case of the substituent R2, as in the case of,
for example, , the attachment position is at the carbon atom markeC1 WCHH.
Table 1: CompounC1s of formula la

wherein R is methyl or ethyl:

What is claimed is:
1. A process for the preparation of a compound of formula I

wherein
R is C1-C6alkyl;
R05 is Hydrogen, C1-C3alkyl, C1-C3haloalkyl or C1-C3alky)-C1-C3alkoxy; Ri is a Ci-C6alkylene, C3-C6alkeny/ene or C3-C6alkynylene chain which may be substituted one or more times by halogen and/or by R5, the unsaturated bonds of the chain not being attached directly to the substituent Xr, R4 is Ci-C4haloalkyI;
X1 is oxygen, -O(CO)-, -(CO)O-, -0(CO)0-, -N(R6)-0-, -ONR17-, thio, suifinyl, sulfonyl, -S02NR7-, -NR18S02-, -N(S02R18a)-, -N(R18b)C(0)- or -NR8-; Ri8a is C1-C6alkyl;
R2 is hydrogen or C1-C8alkyl, or is a C1-C8aIkyl, C3-C6alkenyl or C3-C6alkynyl group which may be substituted one or more times by substituents selected from halogen, hydroxy, amino, formyl, nitro, cyano, mercapto, carbamoyl, C1-C6alkoxy, CrC6alkoxycarbonyl, C2-C6a)kenyl, C2-C6haloalkenyI, C2-C6alkynyl, C2"C6haloalkynyl, C3~C6cycioalkyl, halo-substituted C3-C6cycloalkyl, C3-C6aIkenyioxy, C3-C6aIkynyloxy, CrC6hafoaIkoxy, C3» C6haloaikenyloxy, cyano-C1-C6a!koxy, C1-C6alkoxy-Cr-C6alkoxy, C1-C6alkoxy-C1-C6alkoxy-C1-C6alkoxy, C1-C6alkylthio-C1-C6alkoxy,C1 -C6alkylsulfinyl-C1-C6alkoxy, G,-C6alkylsulfonyl-Cr-C6alkoxy, Cr-C6alkoxycarbonyl-C1-C6alkoxy, C1-C6alkylcarbonyl, C1-C6alkyIthio, C1-C6alkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylthio, C1-C6haloalkylsulfinyl, C1-C6haloalkylsulfonyl, oxiranyl (which may in turn be substituted by C-rC6alkyl), (3-oxetanyI)oxy (which may in turn be substituted by Ci-C6alkyl), benzyloxy, benzylthio, benzylsulfinyl, benzylsulfonyl, CVCealkylamino, di(CrC6alkyI)amino, R9S(0)20-, R10N(R11)S02-, rhodano, phenyl, phenoxy, phenylthio, phenylsulfinyl and phenylsulfonyl;

it being possible for the phenyl-.or benzyl-containing groups to be in turn substituteC1 by one or mora C1-C6alkyl, C1-C6haloalkyl, c1-C6alkoxy, C1-C6haloalkoxy, halogen, cyano, hyC1roxy or nitro groups, or
R2 is phenyl which may be substituteC1 one or more times by C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloalkoxy, halogen, cyano, hyC1roxy or by nitro; or R2 is C3-C6cycloalkyl, C1-C6alkoxy- or C1--C6alkyl-substituteC1 C3-C6cycloalkyI, 3-oxetanyl or C1-C6alkyl-substituteC1 3-oxetanyl; or
R2 is a three- to ten-membereC1, monocyclic or fuseC1 bicyclic, ring system which may be aromatic, partially saturateC1 or fully saturateC1 anC1 may contain from 1 to 4 hetero atoms selecteC1 from nitrogen, oxygen, sulfur, anC1/or may contain the group -C(=0)-, -C(=S)-, -C(=NR19)-,.-(N=0)-, -S(=0)- or -S02-, the ring system being attacheC1 to the substituent Xi either C1irectly or by way of a Ci-C4alkylene, C2-C4alkenylene, C2-C1aIkynylene, -N(R12)-C1-C1aIky)ene, -O-C1-C1alkylene, -S-Ci-C4alkylene, -S0-C1-C4alkylene or -S02-C1-C4aIkyIene group anC1 each ring system containing no more than 2 oxygen atoms anC1 no more than two sulfur atoms, anC1 it being possible for each ring system itself to be substituteC1 one or more times by C1-C6alkyi, C1C6haloalkyl, C2-C6alkenyl, C2-C6halo-alkenyl, C2-C6alkynyl, C2-C6haloalkynyl, C1-C6alkoxy, Ci-C6haloaIkoxy, C3-C6alkenyloxy, C3-C6alkynyIoxy, mercapto, amino, hyC1roxy, C1-C1>alkyIthio, C1-C6haloa!kylthio, C3-C6-alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C-rC3alkoxy-C1-C1alkylthio, C1-C4alkyI-carbonyl-C1-C3alkylthio, C1-C1alkoxycarbonyl-C1-C3alkylthio, cyano-C1-C3alkylthio, C1-C6-alkylsulfinyl, C1-C6haloalkylsulfinyI, C1-CealkylsuIfonyl, C1-C6haloalkylsulfonyl, amino-sulfonyl, C1-C2a!kylaminosulfonyl, N,N-C1i(C1-C2alkyI)aminosulfonyI, C1i(C1-C1alkyI)amino, halogen, cyano, nitro or by phenyl, it being possible for the phenyl group to be in turn substituteC1 by hyC1roxy, C1-C6alkyIthio, C1-C1>haloalkylthio, C3-C6alkenylthio, C3-C6halo-alkenylthio, C3-C6aIkynylthio, C1C3alkoxy-C1-C3alkyIthio, C1-C1a!kylcarbonyl-C1-C3alkyl-thio, C1C4alkoxycarbonyl-C1C3aIkylthio, cyano-C1-C3alkylthio, C1C1alkylsulfinyl, C1-C6-haloalkylsulfinyl, C1-C6alkylsulfonyl, C1C6haloaIkylsu!fonyl, aminosulfonyl, C1-C2alkyl-aminosulfonyl, N,N-C1i(C1-C2alkyl)aminosulfonyl, C1i(C1-C4alkyl)amino, halogen, cyano or by nitro, anC1 the substituents on nitrogen in a heterocyclic ring being other than halogen; R5 is hyC1roxy, C1-C6alkoxy, C3-C6cycIoaIkyloxy, C1-C6alkoxy-C1-C6alkoxy, C1-C6a!koxy-C1-C6aIkoxy-C1-C6alkoxy or C1-C2aIkylsulfonyioxy;
Re, R-, RB, RQ, R10 R11, RI2, R17, RIS anC1 R18b are each inC1epenC1ently of the others hyC1rogen, C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxycarbonyI, C1-C6alkylcarbonyl, C1-C6-alkoxy-Ci-C6alkyl, C1-C6alkoxy-C1-C6alkyI substituteC1 by C1-C6alkoxy, benzyl, or phenyl, it

being possible for phenyl anC1 benzyl to be in turn substituteC1 one or more times by C1.-C6alkyl,,C1-C6haloalkyl, C1-C6alkoxy, C1-C6haloa!koxy, halogen, cyano, hyC1roxy or by nitro; R6 not being hyC1rogen when R9 is hyC1rogen, C1-C6alkoxycarbonyl or C1-C6alkyI-carbonyl;
or the group -RrX1-R2 together is C1-C6alkyl, C2-C6alkenyl, C2-C6haloaIkenyl, C2-C6-alkynyl, C2-C6haloaIkynyI, C3-C6cycloalkyl, C1-C6alkoxy, C1C6haloalkoxy, C1-C6alkylthio, C1-C6aIkylsulfinyl, C1-C6alkylsu!fonyl, C1-C6haloa!kyl, C1-C6haloa!kyIthio, C1-C6haloalkyI-sulfinyl, C1-C6haloalkylsulfonyl, C1-C6alkoxycarbonylf C1C6aIkylcarbonyl, C1-C6alkylamino, C1i(C1-C6alkyl)amino, C1-C6alkylaminosulfonyl, C1i(C1-C6alkyl)aminosulfonyl, -NH-S-R13, -N-(C1-C1alky(thio)-R13, -NH-SO-R14, -N-(C1-C4alkylsulfonyl)-R14, -NH-S02-R15, -N-(C1-C4alkylsulfonyl)-Ri5, nitro, cyano, halogen, hyC1roxy, amino, formyl, rhoC1ano-C1-C6-alkyl, cyano-C1-C6alkyl, oxiranyl, C3-C6alkenyloxy, C3-C6alkynyloxy, C1-C6alkoxy-C1-C1r alkoxy, cyano-C1-C6alkenyloxy, C1-C1alkoxycarbonyloxy-C1-Cealkoxy, C3-C6alkynyloxy, cyano-C1-C6alkoxy, C1-C6alkoxycarbonyl-C1-C1ialkoxy, C1-C1>alkylthio-C1-C6aikoxy, C1-C6alkoxycarbonyl-C1-C6alkylthio, C1-C1aIkoxycarbonyKXrC1>alkyIsulfinyl, C1-C6alkoxycarbonyI-C1-C6alkylsulfonyl, C1~C6alkyIsulfonyIoxy, C1-C6haIoalky!sulfonyloxy, phenyl, benzyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, benzylthio, benzylsulfinyl or benzylsulfonyl, it being possible for the phenyl groups to be substituteC1 one or more times by halogen, methyl, ethyl, trifluoromethyl, methoxy or by nitro; or the group -R1-X1-R2 together is a three- to ten-membereC1, monocyclic or fuseC1 bicyclic, ring system, which may be aromatic, partially saturateC1 or saturateC1 anC1 which may contain from 1 to 4 hetero atoms selecteC1 from nitrogen, oxygen anC1 sulfur anC1/or may contain one or two groups selecteC1 from -C(=0)-, -C(=S)-, -C(=NR20)-, -(N=0)-, -S(=0)-anC1 -S02-, the ring system either being attacheC1 to the pyriC1ine ring C1irectly via a carbon atom or being attacheC1 to the pyriC1ine ring via a carbon atom or via a nitrogen atom by way of a C1-C1alkylene, C2-C4alkenyl or C2-C4alkyny! chain, anC1 it being possible for each ring system to contain no more than 2 oxygen atoms anC1 no more than two sulfur atoms, anC1 it being possible for the ring system itself to be substituteC1 one, two or three times by substituents selecteC1 from C1C1alkyl, C1C6haloalkyl, C3-C1>aIkenyl, C3-C6haloalkenyl, C3-Cealkynyl, C3-C6haloalkynyl, C3-C6cycloalkyl, hyC1roxy, C1-C1>a!koxy, C1-C6haloalkoxy, C1r C6alkenylC1xy, C3-C6alkynyloxy, mercapto, C1-C6alkylthio, C1-C1>haloa!kylthio, C3-C6alkenylthio, C3-C1>haloalkenylthio, C1-C1alkynylthio, C1-C3alkoxy-C1-C3alkylthio, C1-C3alkylcarbonyl-C1-C3alkylthio, C1-C1a!koxycarbonyI-C1-C3alkylthio, cyano-C1-C3alkylthio, C1-C6alkylsulfinyl, C1-C6haloalkylsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsulfonyl,

aminosulfonyl, C1C2a!kylaminosulfonyl, C1i(C1C6alkyl)aminosulfonyl, C1-C3aIkylene-Rn6, amino, C1-Cealkylamino, C1-C6alkoxyamino, C1i(C1-C6alkyI)amino, (N-C1C6alkyI)-C-,-C6aIkoxyamino, halogen, cyano, nitro, phenyl, benzyloxy anC1 benzylthio, it being possible for phenyl, benzyloxy anC1 benzylthio to be in turn substituteC1 on the phenyl ring by C1 C3alkyl, Ct-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or by nitro, anC1 substituents on a nitrogen atom in a heterocyclic ring being other than halogen; R13 is N(H)-C1-C6alkyl, N(H)-C1C6alkoxy, N-(C1-C6alky!)-C1-C6aIkyl, N-(C1-C6alkyl)-C1-C6alkoxy, C1C6alkoxy, C1-Cehaloalkoxy, C1C6alkyl, C-,-C6haIoalkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C3-C6cycloalkyl or phenyl, it being possible for phenyl to be in turn substituteC1 by C1-C3a!kyl, C1-C1haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or by nitro;
R14 is N(H)-C1C6alkyl, N(H)-C1-C6alkoxy, N-CC1-CealkyO-C1CealkyI, N-(C1-C6alkyl)-C1C6alkoxy, C1C6alkoxy, C1-Cehaloalkoxy, C1-C6alkyl, C1C6haloaIkyl, C3-C6alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C3-C6cycloaIkyl or phenyl, it being possible for phenyl to be in turn substituteC1 by C1-C3a!kyl, C1-C1haloalkyl, C1-C3alkoxy, C1-C3haloa!koxy, halogen, cyano or by nitro;
R15 is N(H)-C1C6alkyl, N(H)-C1-C6alkoxy, N-(C1-C6a)kyl)-C1-C6alky], N-(C1-C6alkyI)-C1-C6alkoxy, C1C6alkoxy, C1-Cehaloalkoxy, C1-C6alkyl, C1-Cehaloalkyl, C1rC1>alkenyl, C3-C6haloalkenyl, C3-C6alkynyl, C3-C6haloalkynyl, C3-C6cycloalkyI or phenyl, it being possible for phenyl to be in turn substituteC1 by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or by nitro;
R16 is C1C3alkoxy? C2-C4alkoxycarbonyl, C1-C3a!kylthio, C1C3alkylsutfinyl, C1-C3alkyl-sulfonyi or phenyl, it being possible for phenyl to be in turn substituteC1 by C1-C3a!kyl, C1-C3haloalkyl, C1-C1alkoxy, C1-C3haloa!koxy, halogen, cyano or by nitro; anC1 R19 anC1 R20 are each inC1epenC1ently of the other hyC1rogen, hyC1roxy, C1-C6alkyI, Cn-Cehaloalkyl, C1C6alkoxy, cyano, C1Cealkylcarbonyl, C1C6alkoxycarbonyl or C1-C6alky)sulfonyl; which process comprises reacting a compounC1 of formula II

wherein R3 is C1-C8alkyl or C3-C6cycloalkyl anC1 R4 anC1 R05 are as C1efineC1 for formula I, with a compounC1 of formula III

wherein R, Ri, R2 anC1 X, are as C1efineC1 for formula I, in an inert solvent in the presence of a proton source.
2. A process accorC1ing to claim 1, wherein there is prepareC1 a compounC1 of formula I
wherein
R4 is halomethyl or haloethyl;
Ros is hyC1rogen;
Xt is oxygen, -O(CO)-, -(CO)O-, -O(C0)0-, -N(R6)-0, -0-NR17-, thio, sulfinyl, suifonyl,
-SO2NR7-, -NR18S02- or -NR8-;
R2 is hyC1rogen or C1-C1»alkyl, or a C1-C8alkyl, C3-C6alkenyl or C3-C6alkynyl group which is
substituteC1 one or more times by halogen, hyC1roxy, amino, formyl, nitro, cyano, mercapto,
carbamoyl, C1-C6alkoxy, C1C1alkoxycarbonyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6-
alkynyl, C2-C6haIoalkynyl, C3-C6cyC1oalkyl, halo-substituteC1 C3-C6cycloalkyl, or by
C3-Cealkenyioxy, C3-C6alkynyloxy, C1-C6haloalkoxy, C3-C6haloalkenyloxy, cyano-
C1C6aIkoxy, C1-Cealkoxy-C1-Cealkoxy, C1Cealkoxy-C1-Cealkoxy-C1Cealkoxy, C1-C6a!kyl-
thio-C-i-Cealkoxy, C1Cealkylsulfinyl-C^Cealkoxy, C1-C6alkylsuIfonyl-C1-C6alkoxy, C1-C6-
alkoxycarbonyl-C1-C6alkoxy, C1-C6alkoxycarbonyl, C1-C6alkylcarbonyl, C1Cealkylthio,
C1Cealkylsulfinyl, C1-C6alkylsulfonyl, C1C6haloalkylthio, C1-C6haIoalkylsulfinyl, C1-C6-
haloalkylsulfonyl, oxiranyl (which may in turn be substituteC1 by C1-C6alkyl), or by
(3-oxetanyl)oxy (which may in turn be substituteC1 by C1-C6alkyl), or by benzylthio,
benzylsulfinyl, benzylsulfonyl, C1-C6alkylamino, C1i(C1C6alkyI)amino, R9S(0)20-,
FlioN(R1i)S02-, rhoC1ano, phenyl, phenoxy, phenylthio, phenylsulfinyl or by phenylsulfonyl;
it being possible for the phenyl- or benzyl-containing groups to be in turn substituteC1 by
one or more C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, C1C6haloalkoxy, halogen, cyano,
hyC1roxy or nitro groups, or
R2 is phenyl which may be substituteC1 one or more times by C1-C6alkyl, C1-C6ha!oalkyl,
C1-C6a!koxy, C1-C6haloalkoxy, halogen, cyano, hyC1roxy or by nitro; or

R2 is C3-C6cyc!oaIkyl, C1-C6alkoxy- or C1C6alkyl-substituteC1 C3-C6cycloaIkyl, 3-oxetanyl or C1C6alkylTsubstituteC13-oxetanyI;
or R2 is a five- to ten-membereC1, monocyclic or fuseC1 bicyclic, ring system which may be aromatic, partially saturateC1 or fully saturateC1 anC1 may contain from 1 to 4 hetero atoms selecteC1 from nitrogen, oxygen, sulfur, anC1/or may contain the group -C(=0)-, -C(=S)-> -C(=NR19)-, -(N=0)-, -S(=0)» or -S02-, the ring system being attacheC1 to the substituent Xi C1irectly or by way of a C1C4alkylene, C2-C4alkenyl-C1-C4alkylene, C2-C4alkynyl-C1C4alkylene, -N(R12)-C1-C4alkylene, -SO-C1-C4alkylene or -S02-C1C4alkylene group anC1 each ring system containing no more than 2 oxygen atoms anC1 no more than two sulfur atoms, anC1 it being possible for each ring system itself to be substituteC1 one or more times by C1.-C6aIkyl, C1-C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyi, C2-C6alkynyl, C2-C6hafoaIkynyl, C1-C6alkoxy, C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyIoxy, mercapto, amino, hyC1roxy, C1-C6alkylthio, C1-C1>haloalkylthio, C3-C6aIkenylthio, C3-C6halo-alkenylthiC1, C3*C6alkynylthio, C1-C1aIkoxy-C1C3aIkylthio, C1C4alkylcarbonyl-C1-C3alkyl-thio, C1C4alkoxycarbonyl-C1C3alkylthio, cyano-C1-C3alkylthio, C1C6alky)sulfinyl, C1C6haloalkyIsulfinyl, C1-C6alkylsulfonyl, C1-C6haloalkylsuIfonyI, aminosulfonyl, C1C2alkylaminosulfonyl, N,N-C1i(C1C2alkyl)aminosulfonyl, C1i(C1-C4a)kyl)amino, halogen, cyano, nitro or by phenyl, it being possible for the phenyl group to be in turn substituteC1 by hyC1roxy, C1-C6alkylthio, C1-C1>haloa!kylthio, QrCealkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C1-C1alkoxy-C1-C3alkylthio, C1-C1alkylcarbonyl-C1-C3aIky)thio, C1C1-alkoxycarbonyl-C1-C3alkylthio, cyano-C1C3alkylthio, C1C6aIkylsulfinyl, C1-C6ha!oalkyI-sulfinyl, C1-Cealkylsulfonyl, C1-C6haloalkylsuIfonyl, aminosulfonyl, C1C2alkylaminosulfony!, N,N-C1i(C1-C2a!kyl)aminosulfonyl, C1i(C1C1a(kyl)amino, halogen, cyano or by nitro, anC1 the substituents on nitrogen in a heterocyclic ring being other than halogen; Re, R7, Rs> R9, R10 R11, Ria, R17 anC1 Ri8 are each inC1epenC1ently of the others hyC1rogen, C1-C6alkyl, C1-C1shaloalkyl, C1C6alkoxycarbonyl, C1-C6alkylcarbonyl, C1C6alkoxy-C1-C6alkyl, C1C6alkoxy-C1C6alkyl substituteC1 by C1C6alkoxy, benzyl, or phenyl, it being possible for phenyl anC1 benzyl to be in turn substituteC1 one or more times by C1-C6alkyl, C1-C6haloalkyl, C1C6alkoxy, C1-C6haloalkoxy, halogen, cyano, hyC1roxy or by nitro; R6 not being hyC1rogen when R9 is hyC1rogen, C1-Cealkoxycarbonyl or C1-C6a)kyIcarbonyl; or the group -R1-X1-R2 together is C1-C1alkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6-alkynyl, C2-C6haloalkynyl, C3-C6cycloalkyl, C1C6alkoxy, C1C6haloalkoxy, C1-C6aIkylthio, C1C6alkyIsulfinyI, C1C6alkylsulfonyl, C1C6haloaIkyl, C1-C6haloatkylthio, C1-C6ha!oalkyI-sulfinyf, C1-C6haloa!kyIsuIfonyI, C1C6alkoxycarbonyl, C1-C6alkylcarbonyl, C1C6alkylamino,

C1i(C1C6alky!)amino, C1-C6aIkylaminosulfonyl, C1i(C1-C6alkyI)aminosuIfonyl, -NH-S-R13,
-N-(C1C4aIky!thio)-R13? -NH-SO-R14, -N-(C1-C1alkylsuIfonyI)-R14, -NH-SO2-R15,
hi
-N-(C1-C4alkyisulfonyl)-R15, nitro, cyano, halogen, hyC1roxy, amino, formyl, rhoC1ano-C1-C6alkylf cyano-C1-C6alkyl, oxiranyl, C3-C6alkenyloxy, C1-C6alkynyloxy, C1-C6alkoxy-C1C6a!koxy, cyano-C1-C6alkenyloxy, C1-C6alkoxycarbonyloxy-C1-C1;aikoxy, C3-C6alkynyl-oxy, cyano-C1-C1alkoxy, C1-C6alkoxycarbonyl-C1-C6aIkoxy, C1-C6alkylthio-C1-C6aIkoxy, a!koxycarbonyI-C1-C6alkylthio, alkoxycarbonyl-C1-C1>alkylsulfinyl, alkoxycarbonyl-C1-C6alkylsulfonyl, C1-C6alkylsulfonyloxy, C1-CehaloalkylsuIfonyloxy, phenyl, benzyl, phenoxy, phenylthio, phenylsulfinyl, phenylsulfonyl, benzylthio, benzylsulfinyl or benzylsulfonyl, it being possible for the phenyl groups to be substituteC1 one or more times by halogen, methyl, ethyl, trifluoromethyl, methoxy or by nitro;
or the group -Ri-X1-R2 together is a five- to ten-membereC1, monocyclic or fuseC1 bicyclic, ring system, which may be aromatic or partially saturateC1 anC1 which may contain from 1 to 4 hetero atoms selecteC1 from nitrogen, oxygen anC1 sulfur, the ring system either being C1irectly attacheC1 to the pyriC1ine ring or being attacheC1 to the pyriC1ine ring by way of a C1C1alkylene group, anC1 it being possible for each ring system to contain no more than 2 oxygen atoms anC1 no more than two sulfur atoms, anC1/or to contain the group -C(=0)-, -C(=S)-, -C(=NR2oK -(N=Oh -S(=0)- or -S02-;
anC1 the ring system itself may be substituteC1 one, two or three times by C1-C6alkyl, C-rQe-haloalkyl, C3-C6alkenyl, C3-C6haloaIkenyl, C1rC1alkynyl, C3-C6haloalkynyl, C1C6alkox/,;! C1-C6haloalkoxy, C3-C6alkenyloxy, C3-C6alkynyloxy, mercapto, C1C6aikylthio, C1-C6- i haloalkylthio, C3-C6alkenylthio, C3-C6haloalkenylthio, C3-C6alkynylthio, C2-C5alkoxyalkyl-| Mo, C3-C5acetylalkylthio, C3-C6alkoxycarbonylalkylthio, C2-C1cyanoalkylthio, C1-C6alkyI-sulfinyl, C1C6haloaIkylsulfinyl, C1-C6alkylsulfonyl, (VCehaloalkylsulfonyl, aminosulfonyl, C1-C2aIkylaminosulfonyl, C2-C1C1ialkylaminosulfonyI, C1-C3alky!ene-R16, N(H)~C1-C6alkyl, N(H)-C1-C6aIkoxy, N-(C1C6alkyl)-C1-C6alkyl, N-(C1-CealkyI)-C1-C^lkoxy, halogen, cyano, nitro, phenyl anC1 by benzylthio, it being possible for phenyl anC1 benzylthio to be in turn substituteC1 on the phenyl ring by C1-C3alkyl, C1-C3haloalkyl, C1-C3alkoxy, C1-C3haloalkoxy, halogen, cyano or by nitro, anC1 substituents on nitrogen in a heterocyclic ring being other than halogen; anC1
R19 anC1 R2o are each inC1epenC1ently of the other hyC1rogen, hyC1roxy, C1-C6aIkyI, C1-C6-haloalkyl, C1-C6alkoxy, C1-C6alkylcarbonyl, C1C6alkoxycarbonyl or C1-C6aIkylsulfonyl.

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Patent Number

227375

Indian Patent Application Number

2175/CHENP/2005

PG Journal Number

07/2009

Publication Date

13-Feb-2009

Grant Date

07-Jan-2009

Date of Filing

06-Sep-2005

Name of Patentee

SYNGENTA PARTICIPATIONS AG

Applicant Address

SCHWARZWALDALLEE 215, CH-4058 BASEL,

Inventors:

#	Inventor's Name	Inventor's Address
1	JACKSON, DAVID, ANTHONY	SYNGENTA CROP PROTECTION MUENCHWILEN AG, BREITENLOH 5, CH-MUENCHWILEN,
2	BOWDEN, MARTIN, CHARLES	SYNGENTA HUDDERSFIELD WORKS, LEEDS ROAD, HUDDERSFIELD WEST YORKSHIRE HD2 1FF,

PCT International Classification Number

C07D213/79

PCT International Application Number

PCT/EP04/02291

PCT International Filing date

2004-03-05

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	373/03	2003-03-07	Switzerland