CA1145342A

CA1145342A - N,n-disubstituted ethylglycine (thiol) esters, processes for their preparation and their use as fungicides

Info

Publication number: CA1145342A
Application number: CA000349522A
Authority: CA
Inventors: Winfried Lunkenheimer; Wilhelm Brandes
Original assignee: Bayer AG
Current assignee: Bayer AG
Priority date: 1979-04-12
Filing date: 1980-04-10
Publication date: 1983-04-26
Also published as: DE3061250D1; DD150420A5; DE2915026A1; IL59783A0; EP0017850B1; ES8101039A1; CS212230B2; DK157280A; PT71051A; NZ193373A; JPS6348862B2; JPS55141451A; AU5732680A; AR226056A1; GR68195B; ZA802185B; EP0017850A1; BR8002253A; PL223369A1; ATE1944T1

Abstract

ABSTRACT OF THE DISCLOSURE
N,N-Distubstituted ethylglycine (thiol) esters of the formula

Description

~L45~

The present invention relates to certain new N,N-disubstitutea ethylglycine (thiol)esters, to a process for their preparation and to their use as fungicides.
It has already beeTI disclosed that such halogenoacetanilides as, for example, N-chloroacetyl-N-(2,6-dialkylphenyl)-alanine alkyl esters and -glycine alkyl esters can be employed with good success for combating fungal diseases of plants (see DT-OS (German Published Specification) 2,350,944 and United States Patent Specification 3,780,090). However, their action is not always completely satisfactory, especially when small amounts and low concentrations are used, and in particular also in combating Phytophthora species.
The present invention now provides, as new compounds, the N,N-disub-stituted ethylglycine (thiol)esters of the general formula R2 Rl f 2H5 1l / CH - C - Y - R

~ N /

R ~C - R
o in which R represents alkyl, hydroxyalkyl, cyanoalkyl, alkenyl, alkynyl, halo-genoalkyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, acyloxy-alkyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl, dialkylamino-alkyl or aralkyl optionally substituted by one or more substituents selected from halogens, cyano, nitro, alkyl with 1 or 2 carbon atoms or halogenoalkyl with 1 or 2 carbon atoms and up to three identical or different halogen atoms;
Rl represents hydrogen, alkyl, alkoxy or halogen; R2 represents hydrogen, alkyl,alkoxy or halogen; R represents hydrogen or alkyl; Y represents oxygen or sulphur and R4 represents furyl, tetrahydrofuryl, thienyl or tetrahydrothienyl;
isoxazolyl which is optionally substituted by alkyl; hydroxyalkyl; alkyl, B

~, , 53~

alkenyl or alkynyl which is optionally subs~ituted by cyano or thiocyano;
cycloalkyl; dihalogenoalkyl; or the grouping -CH2-Az, -CH20R , -CH2-SR , -OP~ , -SR , -CH2-OSO2R , -CH20COR or -CH2-0 ~ wherein R represents an alkyl, alkenyl, alkynyl, which alkyl, alkenyl or alkynyl group is optionally substi-tuted by halogen, cyano or thiocyano, or an alkoxyalkyl group and Az represents pyrazol-l-yl, 1,2,4-triazol-1-yl or imidazol-l-yl.
It has been found that the N,N-disubstituted ethyl-glycine (thiol)-esters of the formula I have powerful fungicidal properties.
Those compounds of the formula I are preferred in which R represents straight-chain or branched alkyl with 1 to 6 carbon atoms; hydroxyalkyl or cyanoalkyl with in either case 1 to 4 carbon atoms in the alkyl part; alkenyl or alkynyl with 2 to 4 carbon atoms; halogenoalkyl with 1 to 4 carbon atoms and up to 5 halogen atoms ~especially with up to 2 carbon atoms and up to 3 identi-cal or different halogen atoms, preferred halogens being fluorine and chlorine);
cycloalkyl with 3 to 7 carbon atoms, cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part and 1 to 4 carbon atoms in the alkyl part; alkoxyalkyl, alkoxyalkoxyalkyl, alkylthioalkyl, alkylsulphinylalkyl 9 alkylsulphonylalkyl or dialkylaminoalkyl with 1 to 4 carbon atoms in each alkyl part; acyloxyalkyl with 1 to 4 carbon atoms in the alkyl part, ~he acyl part having the general formula R7-Co- wherein R denotes alkyl with 1 to 4 carbon atoms, halogenoalkyl with 1 to 4 carbon atoms and up to 5 halogen atoms (especially with up to 2 carbon atoms and up to 3 identical or different halogen atoms, preferred halogens being fluorine or chlorine) or aryl with 6 to 10 carbon atoms or aralkyl with 6 to 10 carbon atoms in the '~3,l - 2 -' ' ' ,. ' , 3 ~'~

aryl part and 1 to 4 carbon atoms in the alkyl part (especially phenyl or benzyl), the aryl radical or the aryl part of the aralkyl radical optionally carrying one or more substituents selected from halogen(especially : fluorine, chlorine andbromine), cyano, nitro, alkyl with 1 to 2 carbon atoms or halogenoalkyl with up to two carbon atoms and up to 3 identical or different halogen atoms (preferred halogens being fluorine or chlorine and tri-fluoromethyl being mentioned as an example); or aralkyl which has 6 to 10 carbon atoms in the aryl part (which is preferably phenyl) and 1 to 4 carbon atoms in the alkyl part, the aryl part optionally carrying one or more substituents selected from halogen (especially fluorine, chlorine and bromine), cyano, nitro, alkyl with 1 or 2 carbon atoms and halogenoalkyl with up to 2 carbon atoms and up to 3 identical or different halogen atoms (pre-ferred halogens being fluorine and chlorine, and tri-fluoromethyl being mentioned as an example), R1 and R2 are identical or different and each re-present hydrogen, straight-chain or branched alkyl or alkoxy with 1 to 4 carbon atoms or halogen (especially ~luorine, chlorine or bromine), R3 represents hydrogen or straight-chain or branched alkyl with 1 to 4 carbon atoms, Y represents oxygen or sulphur, R represents furyl~ tetrahydrofuryl, thienyl or tetrahydrothienyl; isoxazolyl which is optionally sub-stituted by methyl or ethyl; hydroxyalkyl with 1 to 2 carbon atoms; alkyl with 1 to 4 carbon atoms,optionally substituted by cyano or thiocyano; alkenyl or alkynyl with in either case 2 to 4 carbon atoms, optionally substituted by cyano or thiocyano, cycloalkyl with 3 to 7 carbon atoms; dihalogenoalkyl with 1 to 2 carbon atoms (preferred halogen atoms being fluorine and chlorine)~
or the grouping -CH2-Az, -CH2-oR5~ -CH2-SR5, -oR5, Le A 19 573 -SR5, -CH2-oSo2R5, -CH20CoR5 or -CH2-0 ~ 3 Az rep~esents pyrazol-l-yl, 1,2,4-triazol-1-yl o~
imidazol-l-yl, and R5 represents alkyl with 1 to 4 carbon atoms or alkenyl or alkynyl with in each case 2 to 4 carbon atoms, in each case optionally substituted by halogen (especially fluorine, chlorine or bromine), cyano or thiocyano, or represents alkoxyalkyl with 1 to 4 carbon atoms in each alkyl part.
The invention also provides a process for the preparation of an N,N-disubstituted ethylglycine (thiol)-ester of the formula (I) in which (a) an N-phenyl-ethylglycine (thiol) ester of the general formula C~ H~ 0 R2 ~ ~ H - C - Y - R (II), in which R, Rl, R2, R3 and Y have the meanings indicated above, is reacted with an acid chloride, bromide or anhydride of the general formula R4 - C - Cl(Br) (IIIa) o or (R - C -)2 (IIIb), in which R4 has the meaning indicated above, in the pre3ence of a diluent and if appropriate in the presence of an acid-binding agent 3 or (b) an N-acyl-N-phenyl-ethylglycine of the general formula Le A 19 573 tzHso R2 ~ R' ~CH- C - O - H
~ N (IV)~

o in which Rl, R2, R3 and R4 have the meanings indicated above, 5 is reacted with an alcohol or thiol of the general formula R - Y - H (V), in which R and Y have the meanings indicated above, in the presence of a condensing agent and if appropriate in the presence Or a diluent, or (c) an N-acyl-N-phenyl-ethylglycine chloride of the general formula C2H~
R2~, CH- 9 Cl (VI), R3 \ ~ ~ R~
in which Rl' R2' R3 and R4 have the meanings indicated above, is reacted with an alcohol or thiol of the formula (V) in the presence of a diluent and if appropriate in the presence of a base, or (d) an N-halogenoacetyl-N-phenyl-ethylglycine (thiol)ester of the general formula c2~
R2 ~ R~ ~ CH- ~ - Y - R (VII), R3 ~ \ ~ - CH2 - Hal Le A 19 573 s~

in which R, Rl, R2, R3 and Y have the meanings indicated above and Hal represents chlorine, bromine or iodine 3 is reacted with a compound of the general formula B - X (VIII), in which X represents Az, cyano, thiocyano or the grouping -oR5 or -SR5 or alkoxycarbonyloxy with 1 to 4 carbon atoms in the alkyl moiety and B represents hydrogen or an alkali metal, in the presence of a diluent and if appropriate in the presence of an acid-binding agent, or (e) an N-hydroxyacetyl-N-phenyl-ethylglycine (thiol)-ester, according to the invenkion, of the general formula R~ ~ - CH2 - OH

in which R, Rl, R2, R3 and Y have the meanings indicatec.
above, (l) is reacted, if appropriate after activation by means Of an alkali metal, with a halide of the general formula Hal - R6 (X), in which Hal has the meaning indicated above and R~ represents the radical R5 or the group -S02R5 or -COR , wherein R5 has the meaning indicated above, in the presence of a diluent and if appropriate in the presence of an acid-binding agent, or Le A 19 573 , -- 7 ~

(2) is reacted with dihydropyrane, of the formula ~ (XI)~

in the presence of a diluent and if appropriate in the presence of a catalyst.
Process variants (d) and (e) are applicable to the preparation of only certain of the active compounds of the formula (I).
Surprisingly, the N,N-disubstituted ethylglycine (thiol)esters according to the invention display a con-sidera~ly higher action, especially against Phytophthora, than the N-chloroacetyl-N-(2,6-dialkylphenyl)-alanine alkyl esters and -glycine alkyl esters which are known from the state of the art and are closely related com-pounds chemically and from the point of view of their action. The active compounds according to the invention thus represent an enrichment of the art.
The particularly preferred compounds of the formula (I) are those in which R represents methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, hydroxyethyl, cyanomethyl, allyl, propargyl, chloroethyl, cyclopropyl, cyclopropylmethyl, cyclohexyl, cyclohexylmethyl, methoxyethyl, ethoxyethyl, methylthioethyl, ethylthioethyl, methoxyethoxyethyl, chloroacetoxyethJl, methylsulphinylethy], ethylsulphinylethyl, methylsulphonylethyl, ethylsulphonyl-ethyl, benzyl which is optionally substituted by chlorineand/or by methyl andtor by ethyl, dimethylaminoethyl or diethylaminoethyl; R3 represents hydrogen~ methyl, ethyl, n-propyl, lsopropyl, n-butyl, isobutyl, sec.-butyl or tert.-butyl, ~1 and R2 are identical or different and

3 represent hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, methoxy, ethoxy, isopropoxy, fluorine, chlorine or bromine, and R represents Le A 19 573 ~5~

2-furyl, 2-thienyl, 2-tetrahydrofuryl, 5-methylisoxazol-3-yl, methoxymethyl, ethoxymethyl, allyloxymethyl, propargyl-oxymethyl, ethoxymethoxymethyl, methylmercaptomethyl, methoxy, ethoxy, methylmercapto, cyclohexyl, dichloro-methyl, hydroxymethyl, methanesulphonyloxymethyl,acetoxymethyl, propionyloxymethyl, dichloromethyl, pyrazol-l-yl-methyl, imidazol-l-yl-methyl, 1,2,4-triazol-1-yl-methyl or tetrahydropyran-2-yl-oxymethyl.
The following compounds of the general formula (I) may be mentioned specifically, in addition ~o the com-pounds mentioned later in the preparative examples:

R; ~ l2R, O

R1 R2 R3 R~ Y R
.. . . , . . _ . . . .
H H H ~ ~ O -CH3 H H H ~1J -C2H5 H H H 0~ -CH2CH2Cl H H H -~ O -CH2CH2OCH3 H H H ~0~ -CH2CH20C2H~OCH3 H H H ~0~ -CH2CH20COCH2Cl H H H ~ O -CH2-CH=CH2 H H H ~rO~ -CH2-C- CH

H H H ~0 H H H - ~ O -CH

Le A 19 573 34;~

Rl R2 R3 R~ Y
, H H H ~O~ -CH2cH2scH3 H H H ~ O~ O -CH2CH2SOCH3 H H H - ~ O -CH2CH2S02CH3 H H H ~O~ -CH2CHz~N(CH3 )2 H H H ~ O C

H H H rO~ -CH2CN

CH3 6-CH3 H ~ o -C2H3 CH3 6-CH3 H ~ O -CH2CHzCl CH3 6-CH3 H -l~J -CH2cH2ocH3 CH3 6-CH3 H ~ O -cH2cH2oc2H4ocH~

CH3 6-CH3 H ~ ~ O -CH2CH20COCH~Cl CH3 6-CH3 H ~O~ O -CH2-CH=CH2 CH3 6-CH3 H rO~ O CH2-C _ CH

CH3 6-CH3 H ~ O

CH3 6-CH3 H ~ O -CH2 ~

CH3 6-CH3 H ~ ~J O -CH2CH2SCH3 CH3 6-CH3 H ~oJ O -CH2CH2SOCH3 CH3 6-CH3 H ~ O -CH2CH2SO2CH~

Le A 19 573 ~ ' ` ~4S~4~

CH, 6-CH3 H ~ O -C~H2C~H2 -N~C~H3 )a CH3 6-CH3 H ~ O Cl CH3 6-CH3 H ~ ~ J O -CH~ ClN

C~ 6-C2H5 H ~ -CH3 CH3 6-C2 Hs H ~O~ o -C2 Hs CH3 6-C2Hs H ~ -CH2 CH2 Cl CH; 6-C2 H5 H ~ O -CH2 CH2 OCH3 CH3 6-C2 H~ H ' ~ ~ O -CH2 CH2 OC2 H~OCH~

CH3 6-C2 Hs H ~O~ O - ~ 2 CH2 OCOCH2 Cl CH3 6-C2 Hs H ~o J O -CH2 -CH-CH2 CH3 6-C2 Hs H ~ ~ O -CH2 -C - CH

CH3 6-C2H5 H ~ O

CH3 6-C2 Hs H ~ O~ O -CH2 ~

CH3 6-C2H~ H ~ O -CH2 CH2 S~H3 CH3 6-C2Hs H ~ O -CH2 CH2 SOCH3 CH3 6-C2Hs H ~ O -CH2 CH2 SO2 CH3 CH3 6-C2Hs H ~oJ O -CH2 CH2 -N(C'H~ )2 CH3 6-C2 Hs H ~ -CH2cl ~ Cl CH~ 6-CzH~ H ~ O~ O -CHk CN

Le A 19 573 ~ ~s3~2 R' R2 R3 F~4 y R

HHH-CH2-O-CH3 O -CH2CH2Cl HHH-CH2-O-CH3 O -~zCHzOC2H40CH3 HHH-CH2~0-CH3 O -~2C~OCOC~Cl HHH-CH2-O-CH3 O -CH2-CH=CH2 HHH-CH2-O-CH3 O -CH2-C_~

HHH-CH2-O-CH3 O -~2 HHH-CH2-O-CH3 O -~2~2S~
HHH-CH2-O-CH3 O -cH2cH2socH~
HHH-CH20-CH3 O -CH2CH2S~3 HHH-CH2-O-CH3 O ~2~2-N~

HHH-CH2-O-CH3 O Cl~Cl HHH-CH2~0-CH~ O -~a~

LeA19573 Rl R2 R3 R4 Y ~.

CH36-CH3 H -CH2-G-CH30 -CzH~
CH36-CH3 H -CH2-O~CH30 -CH2CH2Cl CH3 6-CH3 H -CH2-O-CH30 -CH2CH20cocH2 CH36-CH3 H -CH2-O-CH30 -CH2-CH=CH2 CH36-CH3 H -CH2-O-CH30 -~H2-C _ CH

CH3 6-CH3 H -CH2-O-CH30 -Cff2 ~

CH36-CH3 H -CH2-O-CH30 -CH2 CH2 -N(CH~ )2 CH3 6-CH3 H -CH2-O-CH30 -CH~l ~ Cl CH~ 6-CH~ H -CH2-O-CH30 -CH~CN

Le A 19 573 .

3~s~

Rl R R R Y R

CH3 6-C2H5 H -CH2-0-CH3 o -CH2CH2Cl CH3 6-C2H5 H-CH2-C~C~3 -CH2CH20C2H40CH3 Ch-3 6-C2H5 H -CH2-0-CH3 o 2 2 2 CH3 6-C2H5 CH2-0-CH3 o 2 CH3 6-C2H5 H -CH2-0-CH3 o -CH2 ~

CH3 6-C2H5 H -CH2-0-CH3 o 2 2 2 3 CH3 6-C2H5 H -CH2-0-CH3 o -CH CH -N(CH ) CH3 6-C2H5 H -CH2-0-CH3 0 -CH2 ~ Cl CH36--C2H5 HaCH2--0-CH3 0 --CH2CN

~53~L~

R' R2 ~3 R~ Y R

H H H -CH2-N ¦ -CH3 \N--H H H -CH2 -~N -C2 H~

H H H -CH2 -~ ¦ O -CHz CH2 Cl H H H -CH2 -N/~ O -CH2 CH2 OCH3 /=
H H H -CH2 -N -CH2 CH2 OC2 H~ OCH~
,/=
H H H -CH2 ~N\N -CH2 CH2 OCOCH2 Cl H H H -5H2 ~NNJ -cH2-cH=cH2 ~=
H H H -CH2 -N 0CH2 -C_ t:H

H H H -CH2-N~ O ~
~1 A
H H H -CH2 -\N ¦ -CH2 ~) r=
H H H -CH2 -N~N O -CH2 CH2 SCH~

H H H -CHz -N -CH2 CH2 SOCH.I

H H H -CH2 -N~ O -CH2 CH2 SO2 ~H3 H H H -C~2 -N~/~ O -CH2 CHe -N ( CH3 )~

H H H -CH2 -1~ O -CH2 ;~Cl H H H -CH2-NN~J ~ t:N

Le A 19 573 .

R' R2 R3 R~ Y R

CH3 6-CH3 H -CH2-N ~ -C2H3 CH3 6-CH3 H -CH2-~ ~ -CH2CH2Cl ~ , CH3 6-CH3 H -CH2-N -CH2CH20C2H~OCH~
CH3 6-CH3 H -CH2-N J o CH2 CH2 ococH2 Cl CH3 6-CH3 H -CH2-N\N -CH2-CH=CH2 CH3 6-CH3 H -CH2-N~ ~ -CH2-C - CH

CH3 6-CH3 H -CH2-~ ~

CH3 6-CH3 H -CH2-N, ~ -CH
/=T
CH3 6-CH3 H -CH2-NN ~ -CH2CH2SCH

CH3 6-CH3 H -CH2-~ ~ -CH2CH2SOCH~

CH3 6-CH3 H -CH2-N~ ~ -CH2CH2SO2CH3 CH3 6-CH3 H -CH2-N~ ~ -CH2CH2-N(CH~)2 CH3 6-CH3 H -CH2-N\ ~ O -CH2 ~ Cl CH3 6-CH3 H -CH2~N O -CH~CN

Le A 19 573 R1 R2 R3 R4 y R

CH3 6-C2H5 H -CHz -N~ ~ -CH3 CH3 6-C2 H5 H -CHz -~ ~ O -C2 Hs CH3 6-C2 H5 H -CH2 -N ~ O -CH2 CH2 Cl CH3 6-C2 H5 H -CH2 -N ~ -CH2 CH2 OCH3 CH3 6-Cz H5 H -CH2 -N J -CH2 CH2 OCz H4 OCH3 CH3 6-C2 H5 H -CH2 -N\ ~ -CH2 CH2 OCO OE ~ Cl CH3 6-C2 H5 H -CH2 -N ¦ -CH2 -CH=CH2 CH3 6-C2 H5 H -CH2 -N ~ -CH2 -C - CH

CH3 6-C2 H5 H -CH2 - ~ O

CH3 6-C2H5 H -CH2 -N\ ~ -CH2 ~

CH3 6-C2 H5 H -CH2 -~ ~ -CH2 CHz SC~3 CH3 6-C2 Hs H -CH2 -~ ~ -CH2 CHzSOCH3 CH3 6-C2 H5 H -CH2 -N ~ O -CH2 CH2SO2 CH3 CH3 6-C2 H5 H -CHz -N~ ~ O -CH2 CH2 -N(CH~ )2 CH3 6-C2 H5 H -CH2 -N ~ -CH2~l ~ Cl CH3 6-C2 H~ H -CH2 -N\ ~ O -CH~C3N

Le A 19 573 ^ 17 -Rl R2 R3 R4 y R

H H H -CHCl2 -CH3 H H H -CHCl2 O -Cz H5 H H H -CHCl2 O -CH2 CH2 OCH3 H H H -CHCl2 O -CH2-CH=CH2 H H H -CHCl2 O -CH2-C_ CH

H H H -CHCl2 O -CH2 CH2 OC2 Hs H H H -CHCl2 O -C2 H4 OC2 H,, OCH3 H H H -CHCl2 O -CH2 CN

CH3 6-CH3 H -CHCl2 _C2 Hs CH3 6-CH3 H -CHCl2 O -CH2 CH2 OCH3 CH3 6-CH3 H -CHCl2 0 -CH2-CH=CH2 CH3 6-CH3 H -CHCl2 O -CH2-C_ CH

CH3 6-CH3 H ~CHCl2 O -CH2 CH2 oC2 Hs C~3 6-CH3 H -CHCl2 O -C2 H~ OC2 H~ OCH3 ~CH3 6-CH3 H -CHCl2 O -CH2 CN

Le A 19 57~

s~
- ln-Cl13 ~,-C2~15 1l -C~iClz -C~13 Cl~3 6-C2 H5 11 -Cl-ICl2 _C2 H5 Cl13 6-C211s H -CIICl2 O -CH2 CH2 OCH3 Cll~ 6-C2~ls H -CIICl2 O -CH -CH=CH2 Cl13 6-C2 H5 }~ -CHCl2 0 -CH2 -C--CH

C~i3 6-C2 H5 H -CHCl2 O -C2 H~ OCz Hs CH3 6-C2 H5 H -CHCl2 0 -C2 H4 OC2 H" OCH3 CH3 6-C2H5 H -CHCl2 O -CH2 CN

H H H -CH2 OCOCH3 O -C2 H~,OC2 H~ OCH3 Le A 19 573 z Rl R2 R3 R4 y R
. . ., ~

~H36-CH3 H -CH2-OCOCH3 0 -CH2CH20CH3 CH36-C~I3 H -CH2-OCOCH3 0 2 C

CH36-C1~3 H -CH -OCOCH O 2 2 2 5 CH36-CH3 H ~ -CCOC 3 -C2H40C2H40CH3 CH36-CH3 H -CH2-OC~CH3 0 ~ CN

~=N
H H-CH2-N = O -CH~
/=N
H H H-CH2 -~ ¦ -C2 H~

H H H-CH2 -N~ O -C2 H~ OCH~
~=N
H H H-CH2-NN¦ O -CH2-CH=CH2 /=N
H H H-CH2-NN~ -CH2-C--CH
/~N
H H H-~H2 ~NN ~ -C2 H" OC2 H, ~N
H H H-CH2 -N I O -C2 H~ OC2 H~ OCH3 ~N
H H H-CH2 N~N~ -CH2 CN
~N
CH3 6-CH~ H-CH2 -~N¦ -C2 H, CH~ 6-CH!~ H-CH2 -N Cl -C2 ~ OCH

CH3 6~ H-cx2-r~ o -CH2-CH=CH2 ~=N
CH~ 6 CH, H~CHa -~N¦ -CH2 -C~ CH
rN
CH3 6-CH3 2 ~N-~ -C2 H~, OC2 H~ -rN

CH~ 6-CH~ H-CH2 -~~ -C;~ H4 OC2 H4 OC}I~
CH3 6~ N~ =~ O -~ CN

Le A 19 57~

.~ ~

Rl R~R3 R~ Y R
f~N

CH36-C2 H5 H-CH2 N JN -C2 H~

CH36-C2 H5 H-CH2-N ~ O -C2H~OCH3 /= N
CH36-C2 H5 H-CH2 -N ~ O -CH2-CH=cH2 CH35-C2 H5 H-CH2 -N ~ O -CH2 -C_ CH
/~N
CH36-C2 H5 H-CH2 -N ¦ O -C2H"OC2Hs /=~N
CH36-C2H5 H-CH2-N ~ -C2 H~ C2 H4OCH3 ~N
CH3 6-C2 H5 H-CH2-N~N~ o -CH2 CN
/=N

CH3 H H-CHCl2 -CH3 Cl 6 CH3 H~ 0~ -CH3 Cl 6-CH3 H~CH2OCH3 -CH3 Cl 6-CH3 H-C~I2-N~N¦ O -CH3 ~ N
Cl 6-CH3 H-CHz-N ¦ Q -CH3 Cl 6-CH3 H-CHCl2 -C~I3 C(C~)3 H H~ J -CH3 C(C~)~ H H-CH2OCH3 -CH3 Le A 19 573 ~L53~2 R' R2 R3 R~ Y R

C(CH3 )3 H H -CH2-N ~ -CH3 ~N
C(CH3)3 H H -CH2-~N ¦ -CH3 C(CH3)3 H H -CHCl2 -CH3 CH3 4-CH3 6-CH3 ~ ~ ~CH3 CH3 4-CH3 6-CH3 -CH2-~ ~ -CH3 ~=~N
CH3 4-CH3 6-CH3 -CH2-NN ¦ -CH3 H H H ~ ~J S -CH3 H H H ~ ~ S ~C2Hg H H H ~ S -CH2-CH=CH2 H H H ~ ~ S -CH2-C~CH
CH~ 6-CH3 H ~a s -CH3 CH3 6-CH3 H ~ S -C2Hs CH3 6-CH3 H rO) S -CH2-CH=CH2 CH~ 6-CH~ H ~ ~J S -CH~ -C8 CH

Le A 19 573 3~2 R' R2 R' R~ Y R
CH3 6-C2Hs H ~ ~ S -CH3 CH, 6-C2H5 H ~ O S -C2Hs CH3 6~C2Hs H ~0~ S -CH2-CH=CH2 CH3 6-C2Hs H ~ ~ S -CH2-C - CH
Cl 6-CH3 H ~ o3 S -CH3 Cl 6-CH3 H ~ S -C2Hs Cl 6-CH3 H ~ 0~ S -CH2-CH=CH2 Cl 6-CH3 H ~ 0~ S -CH2-C _ CH2 CH3 H H ~~OJ S -CH3 CH3 H H -~J s -C2 H5 CH3 H H ~ ~ ~ S -CH2-CH=CH2 CH3 H H ~ ~ J S -CH2-C- CH
C(CH3)3 H H - ~J S ~CH3 C(CH3)3 H H rO~ S -C2Hs C(CH3)3 H H ~0~ S -CH2 CH=CH2 C~CH,)3 H H ~oJ S -CH2-C-- CH

Le A 19 573 53~2 R' R2 R3 R~ Y R
~ . . , CH3 4-CH3 6-CH3 S -CH2-CH=CH2 H H H -CH2OCH3 S -C2Hs H H H -CH2OCH3 S -CH2-CH=CH2 H H H -CH20CH3 S -CH2-C_ CH

CH3 6-CH3 H -CH2OCH3 S -C2Hs CH3 6-CH3 H CH2OCH3 S -CH2-CH=CH2 CH3 6-CH3 H -CH2OCH3 S -CH2-C_ CH

CH3 6-C2H3 H -CH2OCH3 S -C2Hs CH3 6~C2H5 H -CH2OCH3 S -CH2-CH=CH2 CH~ 6-C2H5 H -CH2OCH3 S -CH2-C - CH

Le A 19 573 ~5~2 R' R2 R3 R~ Y R
Cl 6-CH3 H -CH2 OCH3 S -CH3 Cl 6-CH3 H -CH2 OCH3 S -Cz Hs Cl 6-CH3 H -CH2 OCH3 S -CH2 -CH=CH2 Cl 6-CH3 H CH2 OCH3 S -CH2-C----CH

CH3 H H -CH2 OCH3 S -CH2 -CH=CH2 CH3 H H -CH2 OCH3 S -CH2 -C_ CH

C(CH3 )3 H H -CH20CH3 S -CH3 C(CH3 )3 H H -CH20CH3 S -C2H5 C(CH3 )3 H H -CH2 OCH3 S -CH2 -CH=CH2 C(CH3 )3 H H -CH20CH3 S -CH2 -C----CH

CH34-CH3 6-CH3-CHz OCH3 S -CH3 CH34-CH3 6-CH3-CH2 OCH3 S -C2 Hs CH34-CH3 6-CH3-CHz OCH3 S -CH2 -CH-CH2 CH~ 4-CH3 6-CH3 -CH2OCH.: S -CH2 -C--CH

Le A 19 573 R' R2 . _ R~ Y R
H H H -CH2-N\ J S -CH3 N
H H H -CH2 -N~N~ S -Cz Hs H H H -CH2-N~ S -CHz~CH=CH2 H H H -CH2-N\~ S -CH2-C----CH

CH3 6-CH3 H -CH2-N\~ S -CH3 CH3 6-CH3 H -CH2 -N~ S -Cz Hs CH3 6-CH3 H -CH2-N\~ S -CH2-CH=CHz CH3 6-CH3 H -CH2 -N\~ S -CH2 -C--CH

Cl 6-CH3 H -CH2-N,/~ S -CH3 N
Cl 6-CH~; H -CH2 -N\ J s -c2 H5 Cl 6-CH3 H -CH2-N ¦ S -CH2-CH=CH2 Cl 6-CH3 H -CH2 ~~ S -CH2-C_ CH
'N
CH3 H H -CH2-N\~ S -CH3 CH3 H H -CH2 -N\~ S -C2 Hs CH3 H H -CH2-N J s -cH2-cH=cH2 CH2 H H -CH2-N\ ¦ S -CH2-C--CH

Le A 19 573 ~ RZ R3 R4 y R

C(CH3)3 H H -CH2-N ¦ S -CH3 C(CH3)3 H H -CH2-N ~ S ~C2Hs C(CH3)3 H H -CH2-N ~ S -CHz-CH=CH2 N

C(CH3)3 H H -CHz-N\ ~ S -CH2-C- CH

CH3 4-CH3 6-CH3 -CH2-N ~ S -CH3 CH3 4-CH3 6-CH3 -CH2-N ~ S -C2H5 CH3 4-CH3 6-CH3 -CH2-N\ ~ S -CH2-CH=CH2 ~H3 4-CH3 6-CH3 -CH2-~ ~ S -CH2-C-- CH

If, for example, N-(2,6-xylyl)~ethylglycine methyl ester and methoxyacetyl chloride are used as starting materials in process variant (a), the course of the reaction can be represented by the following equation:

CH-C-OCH3 Cl-CG~CH~ ~CU3 H -HCl CH3 CH - 3-oCH3 CH3 IC~-CH20CH3 Le A 19 573 3~

If, for examplé, N-dichloroacetyl-N-(2,6-xylyl)-ethylglycine and propargyl alcohol are used as starting materials and DCC is used as the condensing agent in process variant (b), the course of the reaction can be represented by the following equation:

~CH3 / CH - C-OH +DCC*
N\ + HO-CH2-C- CH -DCH*
CH C - CHCl2 CH3 CH ~ C-O-CH2-C- CH

CH, ~ ~

*DCC = Dicyclohexylcarbodiimide *DCU = Dicyclohexylurea If, for example, N-(2-furoyl)-N-(2,6-xylyl)-ethyl-glycine choride and O-methylglycol are used as starting materials in process variant (c), the course of the reaction can be represented by the following equation:
ÇzH5 CH3 ~H - ~-Cl Ho_cH2CH2-OCH3 \ ~ ~ ~ ~
CH3 CH - ~_o-cH2cH2ocH3 ~ ' c l~J

If, for example, N-chloroacetyl-N-(2,6-xylyl)-ethyl-glycine methyl ester and imidazole are used as starting materials in process variant (d), the course of the reaction can be represented by the following equation:
C2H, ~ CH ~ C-CHz-~

Le A 19 573 5~

CH - g-OCH

CH3 IC~-CHz-N~

If, for example, N-hydroxyacetyl-N-(2,6-xylyl)-ethyl-glycine methyl ester and ethoxymethyl chloride are used as starting ~aterials in process variant (e)(1), the course o~` the reactiorl can be represented by the followin~ equation:

CH ICz~ O ~ ase CH3 C-CH2-OH + Cl-CH2-O-C2H~ -PCl CzH~ 8 N\
CH ICI_CH2-O-CH2-O-C2H5 If, for example, N-hydroxyacetyl~N-(2,6-xylyl)-ethyl-glycine methyl ester and 3,4-dihydro-4H-pyrane are used as starting materials in process variant (e)(23, the course of the reaction can be represented by the following equation:
C2H~
,CH3 CH ~ C-OCH~ O

CH~ C-CH2-OH

~H - C-OC

CH~ ~-CH2_ Le A 19 573 , . . .

z The formula ~II) provides a general definition of the N-phenyl-ethylglycine ~thiol)esters required a3 ~tar~ing materials in carrying out process variant (a). In this formula, R, Rl, R , R3 and Y preferably have those meanings which have already been mentioned as preferred in connection with the description of the compounds of the formula (I).
Some of the N-phenyl-ethylglycine (thiol)esters of the formula (II) have been described in the literature (see U.S. Patent Specification 4,096,167 and DE-OS (German Puh-lished Specification) 2,805,525). They can be obtained by reacting corresponding anilines with corresponding a-halogeno-butyric acid (thiol)esters in the presence of an acid-binding agent~ for example potassium carbonate, and in the presence of an inert organic solvent, for example dimethylformamide, and if appropriate in the presence of a catalyst, for example potassium iodide, at temperatures between 20 and 100C.
The N-phenyl-ethylglycine (thiol) esters of the formula (II) can also be obtained when N-phenyl-ethyl-glycines are esterified with corresponding alcohols orthiols by known processes, for example in the presence of boron trifluoride (in this context, see also the statements for process variant (b)).
Examples of the starting materials of the formula (II) which may be mentioned are:

H~ 0 ~; ~ ~ CH - C - Y - R (II) R~ R2 R3 y R
H H H O(S) -CH3 H H H O(S) -C2H5 H H H O(S) -CH2CH2-0-CH3 H H H O(S) -CH2-CH=CH2 H H H O(S) -CH2-C -- CH

Le A 19 573 ~53~2 ..... Rl.' ',' ', .' '.''.. ' ',' '.R2.''.. '','' ' ' '' .~,3 '' '' ' 'Y ' '' ' ' ' 'R '' '' '' '' '' ' ' '' '' '' .. .. .. . . ~
H H H O(S) -CH2 CH2 -O-C2H5 H H H O ~ S ) -C2 H~-O-C2H~ -OCH3 CH3 6-CH3 H O(S) -CH3 CH3 6-CH3 H O(S) -C2Hs CH3 6-CH3 H O(S) -CH2 CH2 -O-CH3 CH3 6-CH3 H O(S) -CH2-CH=CH2 CH3 6-CH3 H O(S) -CH2-C - CH
CH3 6-CH3 H O(S) -cH2cH2-o-c2Hs CH3 6-CH3 H O(S) -C2H~-O-CzH4-OCH3 C2H5 6-c2H5 H O(S) -CH3 C2H5 6-c2H5 H O(S) -C2H5 C2H5 6-C2H5 H O(S) -CH2CH2 O-CH3 C~H5 6-C2H5 H O(S) -CH2-CH=CH2 C2H~ 6-CzH5 H O(S) -CH2-C - CH
~2H5 6 C2HS H O(S) -cH2cH2-o-c2Hs C2H5 ~-C2H5 H O(S) -C2H~-O-C2H4-OCH3 C2H5 6-CH3 H O(S) -CH3 C2H5 6-CH3 H O(S) -C2Hs C2H~ 6-CH3 H O(S) -CH2CH2-O-CH
C2Hs 6-CH3 H O(S) -cH2~cH=GH2 C2H~ 6-CH3 H O(S) -CH2-C - CH
C2Hs 6-CH3 H O(S) -cHzcH2-o-c2Hs C2 H5 6-CH3 H O(S) -C2H4-O-C2 H4 -OCH3 C(CH3)3 H H O(S) -CH3 C(CH3)3 H H O(S) -C2H5 C(CH3 )3 H H O(S) -CH2 CH2 -O-CH3 C(CH3 )3 H H O(S) -cH2-cH=cH2 C(CH3 )3 H H O(S) -CH2-C----CH
C(CH3 )3 H H O(S) -CH2CH2-O-C2H~
Le A 19 573 4S~
~ 32 -... R .... :.R ....... R~ Y R
C(CH3 )3 H H O(S) -C2H"-O-C2H4-OCH3 CH3 3-CH3 H O(S) -CH3 CH3 3-CH3 H O(S) ~C2Hs CH3 3-CH3 H O ( S ) -CH2 CH2 -O-CH3 CH3 3-CH3 H O ( S ) -cH2 -CH=C~I2 CH3 3-CH3 H O ( S ) -CH2 -C CH
CH3 3-CH3 H O ( S ) -CH2 CH2 -O-C2 H~
CH3 ~-CH3 H O ( S ) -C2 H" -O-C2 H" -OCH3 C2H5 H H O(S) -CH3 C2H~ H H O(S) -C2H5 Cz H5 H H O ( S ) -CH2 CH2 -O-CH3 C2 H~ H H O ( S ) -CH2 -CH=CH2 C2Hs H H O(S) -CH2-C_ CH
C2 Hs H H O ( S ~ -CH2 CH2 -O-C2 H~ -C2H~ H H O(S~ -C2H~ O-C2H"-OCH3 i-C~ H7 H H O ( S ) -CH3 i-C3H7 H H O(S) -C2H~
i-C3H7 H H O(S) ~ CH7CH2-0-CH3 i -C3 H7 H H O ( S ) -CH2 -CH=CH2 i-C~s H7 H H O ( S 3 -CH2 -C--CH
i -C3 H7 H H O ( S ) -CH2 CH2 --C2 H3 i-C3 H7 H H O ( S ) -C2 H4 -O-C2 H" -9CH;
CH3 5-CH3 H O ( S ) -CH3 CH3 5-CH3 H O(S) -C2H, CH3 5-CH3 H O ( S ) -CH2 CH2 -O-CH~
CH3 5-CH3 H O ( S ) -CH2 -CH=CH2 CH3 5-CH3 H O(S) -CH2~C CH
CH3 5-CH3 H O ( S ) -CH2 CH2 -O-C2 H~
CH3 5-CH3 H O ( S ) -C2 H~ ~O~C~ H~ -OCH, Le A 19 573 ~534 R2, .;R3 y .R : :
: ,..... . . .
Cl 6-CH3 H O(S) -CH3 Cl 6-CH3 H O(S) -C2H~
Cl 6-CH3 H O(S) -CH2CH~-O-CH3 Cl 6-CH3 H O(S) -CH2-CH=CH2 Cl 6-CH3 H O(S) -CH2-C_ CH
Cl 6-CH3 H O(S) CH2CH2-O-C~H~
Cl 6-CH3 H O(S) -C2H4-O-C~H~-OCH~
Cl 6-C(CH3)3 H O(S) -~H, Cl 6-C(CH3)3 H O(S) -C2H~
Cl 6-C(CH3)3 H O(S) -CH2CH2-0-CH3 Cl 6-C(CH3)3 H O(S) -CH2-CH=CH2 Cl 6-C(CH3)3 H O(S) -CH2-C- CH
Cl 6-C(CH3)3 H O(S) -CH2CH2-O-C2H5 Cl 6-C(CH3)3 H O(S) -C2H~-O-C2H~-OCH~
CH3 ~-CH3 6-CH3 O(S) -CH3 CH3 3-CH3 6-CH3 0(S) -C2H~
CH3 3-CH3 6-CH3 O(S) -CH2CH2-O-CH3 CH3 3-CH3 6-CH3 O(S) CH2-CH-CHz CH3 3-CH3 6-CH3 O(S) -CH2-C - CH
CH3 3-CH3 6-CH3 O(S) -CH2CH2-O-C2H~
CH3 3-CH3 6-CH3 O(S) -c2H~-o-c2H~-o~H3 CH3 ~-CH3 6-CH3 O(S) -CH3 CH3 4-CH3 6-CH3 O(S) -CzH3 CH3 4-CH3 6-CH3 O(S) -CH2CH2-O CH~
CH3 4-CH3 6-CH3 O(S) -CH2-CH=CH2 CH3 4-CH3 6-CH3 O(S) -CH2-C_ CH
CH3 4-CH3 6-CH3 O(S) -CH2CH2-O-C2H~
CH3 4-CH3 6-CH~ O(S) -C~H~-O-C2H4-OSH~

Le A 19 573 Rl R2 R3 Y R

i-C3 H76-i-Ç3 H7 H O(S) -CH3 i-C3 H76-i-C3 H7 H O(S) -C2 H, i-C3 H76-i-C3 H7 H O(S) CH2 CH2 -O-CH3 -i-C3 H76-i-C3 H7 H O(S) -CH2 -CH-CH2 i-C3 ff76-i-C3 H7 H O(S) -CH2 -C - CH
i-C3 H76-i-C3 H7 H O(S) -CH2 CH2 -O-C2H
i-C3 H76-i -C3 H7 H O(S) -C2 H~ -O-C2 H~ OC~I~
OCH3 6-CH3 H O(S) -CH3 OCH3 6-CH3 H O(S) -C2 H~
OCH3 6-CH3 H O(S) -CH2 CH2 -O-CH3 OCH3 6 CH3 H O(S) -CHz -CH=CH2 OCH3 6-CH3 H O(S) -CH2 -C C~H
OCH3 6-CH3 H O(S) -CH2 CH2 -O-C2 H3 OCH3 6-CH3 H O(S) -C2 H~ -O-C2 H~ -OC~I~
Br 6-CH3 H O(S) -CH3 Br 6-CH3 H O(S) ~C2H~
Br 6-CH3 H O~S) -CH2 CH~ -O-C~
Br 6-CH3 H O(S) -CH2 -CH=CH2 Br 6-CH3 H O(S) -CH2 -C _ C~H
Br 6-CH3 H O(S) -CH2C~H~ --~2 ~b Br 6-CH3 H O(S) ~Ca H4 -O-c~ CX~H~

Le A 19 573 R' R2 R3 Y
OCH3 6-OCH3 H O ( S ) -CH3 OCH3 6-oCH3 H 0(~;) -C2HS
OCH3 6-oCH3 H O t S ) -C~12 CH2 -O-CH3 OCH3 6-oCH3 H O ( S ) -cH2 -CH=CH2 OCH3 6-oCH3 H O(S) -CH2 -C_ CH
OCH3 6-OCH3 H O ( S ) -CH2 CH2 --C2 H5 UCH3 S-OCH3 H O(S) -C2H~-O-CzH~-OCH3 The formulae (IIIa) and (IIIb) provide general definitions of the acid chlorides, bromides and anhydrides also to be used as starting materials for process variant (a). In these formulae, R4 preferably has those meanings which have already been mentioned as preferred in connection with the description of the compounds of the formula (I).
The acid chlorides, bromides and anhydrides of the formulae (IIIa) and (IIIb) are generally known compounds of organic chemistry.
The formula (IY) provides a general definition of the N-acyl-N-phenyl~ethylglycines to be used as starting 20 materials for process variant (b). In this formula, Rl, R2, R3 and R4 preferably have those meanings which have already been mentioned as preferred in connection with the description of the compounds of the formula (I).
The N-acyl-N-phenyl-ethylglycines of the formula (IV) 25 have not hitherto been described in the literature. However, they can be obtained in a simple manner by reacting N-phenyl-ethylglycines with acid chlorides of the formula (IIIa) in the presence of an acid-binding agent 3 for example sodium hydroxide solution, and in the presence of an inert organic solvent, ~or example methylene chloride, at temperatures between 0 and 120C.

Le A 19 573 The formula (V) provides a géneral definition of the alcohols and thiols also ~o be used as starting materials for process variants ~b) and (c). In this formula, R and Y preferably have those meanings ~Jhich have already -been mentioned as preferred in connection with the des-cription of the compounds of the formula (I).
The alcohols and thiols of the formula (V) are generally known compounds of organic chemistry.
The formula (VI) provides a general definition of 10 the N-acyl-N-phenyl-ethylglycine chlorides to be used as starting materlals for process variant (c). In this formula, Rl, R2, R3 and R4 preferably have those meanings which have already been mentioned as preferred in con-nection with the description of the compounds of the 15 formula (I).
The N-acyl-N phenyl-ethylglycine chlorides of the formula (VI) have not hitherto been described in the literature. However, they can be obtained in a simple manner by reacting the N-acyl-N-phenyl-ethylglycines of 20 the formula (IV) with, preferably, oxalyl chloride in the presence of dimethylformamide or pyridine.
The formula (VII) provides a general definition of the N-chloroacetyl-N-phenyl-ethylglycine (thiol)esters required as starting materials in carrying out process 25 variant (d). In this formulag R, Rl, R2 and R3 preferably have those meanings which have already been mentioned as preferred in connection with the description of the com-pounds of the formula (I).
Some of the N-chloroacetyl-N-phenyl-ethylglycine 30 (thiol)esters of the formula (VII) have been described in the literature (see U.S. Patent Specification 4,096,167 and DE-OS (German Published Specification) 2,805,525).
They can be obtained, for example, by reacting N-phenyl-ethylglycine (thiol)esters o~ the formula (II) with ~5 chloroacetic acid chlorides analogously to process variant (a).

Le A 19 573 - 37 ~
The formula (VIII) provides a general défini~ion of the compounds also to be used as rurther starting substances for process variant (d). In this formula, Az and R5 preferably have those meanings which have already been mentioned as preferred in connection with the des-cription of the compounds of the formula (I). B pre-ferably represents hydrogen, sodium or potassium.
The compounds of the rormula ~VIII) are generally known compounds of organic chemistry.
The formula (IX) provides a general definition of the N-hydroxyacetyl-N-phenyl-ethylglycine (thiol)esters required as starting materials in carrying out process variant (e). In this formula, R, Rl, R2 and R3 preferably have those meanings which have already been mentioned as preferred in connection with the description of the compounds of the formula (I).
The N-hydroxyacetyl-N-phenyl-ethylglycine (thiol) esters of the formula (IX) are compounds according to the invention. They can also be obtained by a procedure in which (f) an N-acyloxyacetyl-N~phenyl-ethylgycine (thiol) ester of the general formula R3 ~ R~ C - C - Y - R (XII)~

in which ~5 R, Rl, R2 and R3 have the meaning indicated above and R8 represents alkyl with 1 to 4 carbon atoms, is saponified with sodium hydroxide or potassium hydroxide in aqueous or alcoholic solution, for example in methanol or ethanol, at a temperature of from 20 to 60C and, Le A 19 573 5~ ~Z

after acidification wlth a compound o~ the formula (Y), the saponification product is esterified in the pre~ence of an esterification catalyst, for example boron tri-fluoride.
The acyloxyacetylanilides of the formula (XII) are also compounds according to the instant invention and can be obtained according to the process variants (a) resp (d) which are described above.

The formula ~X) provides a general definition of the halides also to be used as starting materials for process variant (eXl).In this formula, R6 and Hal pre-~erably have the meanings indicated in the definition o~
the invention.
The halides of the formula (X~ are generally known compounds of organic chemistry.
The dihydropyrane also to be used as a starting substance for process variant (e)(2) is likewise a known compound of organic chemiætry.
Preferred diluents for the reaction according to process variant (a) are inert organic solvents. These include, as preferences, ketones, such as diethyl ketone, and in particular acetone and methyl ethyl ketone;
nitriles, such as propionitrile 3 and in particular aceto-nitrile; ethers, such as tetrahydrofuran or dioxan;
aliphatic and aromatic hydrocarbons~ such as petroleum ether, benzene, toluene or xylene; halogenated hydrocarbons, ~uch as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene; and esters, such as ethyl acetate.
If appropriate, process variant (a~ can be carried out in the presence o~ an acid-binding agent EhYdrogen chloride Le A 19 573 5~39L2 (bromide) accépto~; an~ o~ ~hé cuBtomary acid~bi~ding agents can be us0d here. These include organic bases~
preferably tertiary amines, for example triethylamine and pyridine; and furthermore inorganic bases, for example alkali metal hydroxides and alkali metal carbonates.
A possible catalyst is, in particular, dimethylformamide.
The reaction temperatures can be varied within a substantial range in carrying out process variant (a).
In general, the reaction is carried out at from 0 to 120C, preferably ~rom 20 to 100C.
In carrying out process variant (a), 1 to 1.5 moles of the compound of the formula (III) and, if appropriate, 1 to 1.5 moles of acid-binding agent are preferably em-ployed per mole of the compound of the formula (II), if R
does not represent hydroxyalkyl. However, if R in the starting compound (II) represents hydroxyalkyl, 2 to 2.5 moles of the compound of the formula (III) and, if appro-priate, 2 to 2.5 moles of acid-binding agent are employed per mole of this compound. Isolation of the resulting compound of the formula (I) is effected in the customary manner.
Preferred solvents for the reaction according to process variant (b) are inert organic solvents. These include, as preferences, aromatic hydrocarbons, such as benzene, toluene or xylene; halogenated hydrocarbons, such as chloroform or methylene chloride; esters, such as ethyl acetate; ethers, such as tetrahydrofuran; or the actual alcohol (thiol) used as one of the reactants.
Process variant (b) is carried out in the presence of a condensing agent; any of the customary condensing agents can be used here, especially dicyclohexylcarbodi-imide (DCC), chloroformic acid ethyl ester or benzene-sulphonyl chloride.
The reaction temperatures can be varied within a substantial range in carrying out process variant (b).

Le _ 40 -In general 3 ~he reaction is carried out at from 5 to 150C, preferably from 20 to 100C, or a~ the boiling point of the solvent used.
In carrying out process variant (b), 2 to 8 moles of alcohol(thiol) and 1 to 2 moles of condensing agent are preferably employed per mole of the compound of the formula (IV). Isolation of the resultant compound of the formula (I) is effected in the customary manner.
Preferred solvents for the reaction according to process variant (c) are inert organic solvents. These include, as preferences, the solvents which have already been mentioned as preferred for process variant (a).
The reaction can be carried out in the presence of an organic or inorganic base; preferred bases are stated abo~re in the paragraph relating to process variant (a).
The reaction temperatures can be varied within a substantial range in carrying out process variant (c).
In general, the reaction is carried out at from 0 to 120C, preferably from 20 to 100C, or at the boiling point of the particular solvent. Equimolar amounts of the reactants are preferably used in carrying out process variant (c). Isolation of the resultant compound of the formula (I) is effected in the customary manner.
Preferred diluents for the reaction according to process variant (d) are inert organic solvents. These include, as preferences, the solvents which have already been mentioned for process variant (a).
If appropriate, the reaction according to process Yariant (d) can be carried out in the presence of an acid-binding agent. It is possible to add any of the inorganic or organic acid-binding agents which can customarily be used, such as an alkali metal carbonate, for example sodium 3o carbonate, potassium carbonate or sodium bicarbonate, or such as a lower tertiary alkylamine, cycloalkylamine or aralkylamine, for example triethylamine or dimethyl-benzylamine, or such as pyridine and diazabicyclooctane.
An excess of azole, when such is used as one of the re~
actants, is preferably used.

Le A 19 573 i3~2 The reaction temperatures`can be varied ~ithin a substantial range in process variant (~). In ~eneral, the reaction is carried out at from 20 to 150C~ preferably at from 60 to 120C. If a solvent is present, the reaction is appropriately carried out at the boiling point of the particular solvent.
In carrying out process variant (d), 1 to 2 moles of the compound of the formula (VIII) and, if appropriate, 1 to 2 moles of acid-binding agent are preferably employed per mole of the compound of the formula (VII). Isolation of the compounds of the formula (I) is effected in the customary manner.
Preferred diluents for the reaction according to process variant (e) are inert organic solvents. These include 3 as preferences, the solvents which have already been mentioned for process variant (a).
If appropriate, the reaction according to process variant (e)(l) can be carried out in the presence of an acid-binding agent. It is possible to add any of the inorganic or organic acid-binding agents which can cus-tomarily be used. These include, as preferences, the compounds which have already been mentioned for process variant (a).
The reaction temperatures can be varied within a substantial range in process variant (e)(l). In general, the reaction is carried out at from 20 to 150C, pre-ferably at the boiling point of the solvent, for example from 60 to 100~.
In carrying out process variant (e)(l), 1 mole of halide of the formula (X) and, if appropriate, 1 to 2 moles of acid-binding agent are employed - i~ appropriate after adding 1 to 2 moles of a strong base, for example an alkali metal hydride - per mole of the compounds of the formula (IX~. In order to isolate the end product~
the reaction mixture is freed from solvent, and water and Le ~ 19 573 i3~2 ,,, an organic solvent are added to thé résidue. The or~anic phase is separated off and worked up in thé customary manner.
According to a preferred embodiment of the process variant (e3(1), an appropriate procedure is to use a hydroxyacetanilide of the formula (IX) as the starting material, to convert this compound into the alkali metal alkanolate in a suitable inert solvent by means of an alkali metal hydride or bromide and to react this alkanolate immediately, without isolation, with a halide of the formula (X), the resultant compound of the formula (I) being obtained in one operation, with elimination of an alkali metal halide.
If appropriate, the reaction according to process variant (e)(2) can be carried out in the presence of a catalyst. Hydrogen chloride is preferably used'for this ~see J.Am.Chem.Soc. 69, 2246 (1947), and ib'ido''70, 41~7 (1948)).
The reaction temperatures can be varied within a substantial range in process variant (e)(2). In general, the reaction is carried out at from 0 to 100C, preferably from 20 to 60C.
Equimolar amounts of the reactants are preferably used in carrying out process variant (e)(2). Isolation of the resultant compound of the formula (I) is effected in the customary manner.
The active compounds according to the invention exhibit a powerful microbicidal action and can be employed in practice for combating undesired micro-organisms.
The active compounds are suitable for use as plant pro-tection agents.
Fungicidal agents in plant protection are employed for combating Plasmo'dio~h'oromy~cetes~ o'mycetes ? Chy't'ridio-m~ce'tes, ~ ,''A's'c'o'my'c'e:tes,' B'a's'i'd'i'o'myc'et'es and e'u't'e'r'o'my'c'e't'es.

Le A 19 573 53~2 The good toleration, by plants, Or the actiYe com-pounds, at the concentrations required ~or combating plant diseases, permits treatment of above-ground parts of plants, of vegetative propagation stock and seedsJ and of the soil.
As plant protection agents, the active compounds according to the invention can be used with particularly good success for combating Oomycetes, for example the pathogen of blight and brown rot of tomato and potato 10 (Phy'to'phthora'infestans). It should be particularly -emphasised that the active compounds according to the invention not only develop a protective action but also a curative/eradicative action. They also have systemic properties. Thus, it is possible to protect plants against fungal attack when the active compound is fed to the above-ground parts of the plant via the soil and the root or via the seed.
The active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, dusting agents, foams, pastes, soluble powders, granules, aerosols, suspension-emulsion concentrates, seed-treatment powders 3 natural and synthetic materials impregnated with active compound, very fine capsules in polymeric substances, coating compositions for use on seed, and formulations used with burning equipment, such as fumigating cartridges, fumigating cans and fumigating coils, as well as ULV
cold mist and warm mist formulations.
These formulations may be produced in known manner~
for example by mixing the active compounds with extenders, that is to say liquid ~r liquefied gaseous or solid diluents or carriers, optionally with the use of surface-active agents, that is to say emulsifying agents andtor dispersing agents and/or foam-forming agents. In the case of the use of water as an extender, organic Le ~ 19 573 S3~2 solvents can, for example, also be used as au%iliary solvents.
As liquid diluents or carriers, especially solvents, 5here are suitable in the main, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatic or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic or alicyclic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone~ methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, or strongly polar solvents~
such as dimethylformamide and dimethylsulphoxide, as well as ~ater.
By liquefied gaseous diluents or carriers are meant liquids which would be gaseous at normal temperature and under normal pressure, for example aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide.
As solid carriers there may be used ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina and silicates. Assolid carriers for granules there may be used crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, 3o and granules of organic material such as sawdust~
coconut shells, maize cobs and tobacco stalks.
As emulsifying and/or foam-forming agents there may be used non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol Le A 19 573 ~1~53 ethers, alkyl sulphonates, alkyl sulphates, aryl sulphona~es as well as albumin hydrolysis products. Dispersing agents include, for example, lignin sulphite waste liquors and methylcellulose.
Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form Or powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs 3 and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general contain from 0.1 to 95 per cent by weight of active compound, preferably from 0.5 to 90 per cent by weight.
The active compounds according to the invention can be present in the formulations or in the various use forms as a mixture with other active compounds, such as fungi-cides, bactericides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth factors~ plant nutrients and agents for improving soil structure.
The active compounds can be used as such or in the form of their formulations or the use forms prepared therefrom by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and ~0 granules. They may be used in the customary manner, for example by watering, immersion, spraying, atomising, misting, vaporising, injecting, forming a slurry, brushing on, dusting, scattering, dry dressing, moist dressing, wet dressing, slurry dressing or encrusting.

Le A 19 ~7~

Especially in the treatment of parts of plants, the active compound concentrations in the use forms can be varied within a substantial range They are, in general, from 1 to 0.0001% by weight, preferably from 0.5 to 0.001%.
In the treatment of seed, amounts of active com-pound of 0.001 to 50 g, preferably 0.01 to 10 g, are generally employed per kilogram of seed.
For the treatment of soil, active compound con-centrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are generally employed at the place of action.
The present invention also provides a fungicidal composition containing as active ingredient a compound of the present invention in admixture with a solid or liquefied gaseous diluent or carrier or in admixture with a liquid diluent or carrier containing a surface-active agent.
The present invention also provides a method of combating fungi which comprises applying to the fungi , or to a habitat thereof, a compound of the present invention alone or in the form of a composition containing as active ingredient a compound of the present invention in admixture with a diluent or carrier.
The present invention further provides crops protected from damage by fungi by being grown in areas in which immediately prior to and/or during the time of the growing a compound of the present invention was applied alone or in admixture with a diluent or carrier.
It will be seen that the usual methods of providing a harvested crop may be improved by the present invention.
m e fungicidal activity of the compounds of this invention is illustrated by the following biotest Le A 19 573 5~2 Examples.
In these Examples, the compounds according to the present invention are each identified by the number (given in brackets) of the corresponding preparative Example, which will be found later in this specification.
The known comparison compound~ are identified as follows:
n ,__<CH3 CH2- C - O - CH~
(A) = ~ ~ C - CH2Cl N-chloroacetyl-N-(2,6-xylyl)-glycine methyl ester (B) = ~ CH~ 0 C2H5 ~ - CH2Cl N-chloroacetyl-N-(2-ethyl-6-methylphenyl)-alanine methyl ester Example A
~ test (tomato)/protective Solvent: 4.7 parts by weight of acetone Emulsifier: 0.~ part by weight of alkylaryl polyglycol ether Water: 95 parts by weight The amount of the active compound required for the de8ired concentration of the active compound in the spray liquid was mixed with the stated amount of solvent and the concentrate was diluted with the stated amount of water which contained the stated ~e A 19 57~

~53~2 amount of emulsifier.
Young tomato plants with 2 to 4 foliage 'leaves were sprayed with the spray liquid until dripping wet. The plants remained in a greenhouse for 24 hours at 20 deg.C and at a relative atmospheric humidity of 70%. The tomato plants were then inoculated with an aqueous spore suspension of Phyto'p'h't'h'o'ra'i~fe's't'ans.
The plants were brought into a moist chamber with an atmospheric humidity of 100% and a temperature 10 of 18-20 deg.c.
After 5 days the infection of the tomato plants was determined. The assessment data were converted to percent infection: 0% meant no infection; 100%
meant that the plants were totally infected~
In this test, for example, the following compounds exhibited a very good action which was significantly superior to that of the compounds (A) and (B) known from the prior art: compounds (12), (1) and (10).
Example B
20 Phytophthora test (tomato)/systemic Solvent: 4.7 parts by weight of acetone Emulsifier: 0~3 part by weight of alkylaryl polyglycol ether Water: 95 parts by weight The amount of active compound required for the desired concentration of the active compound in the watering liquid was mixed with the stated amount of solvent and the concentrate was diluted with the stated amount of water which contained the stated 30 amount of the emulsifier.
Tomato plants grown in standard soil and having 2 to 4 foliage leaves were watered three times in the course of one week with 10 ml of the watering liquid, having the stated concentration of active 35 compound, per 100 ml of soil.

Le A 19 573 ~s~

The plants -treated in this way were inoculated~
after the treatment, with an aqueous spore suspension of Phytoph'thora'infestans. The plants were brought into a humidity chamber at an atmospheric humidity of 100% and a temperature of 18 to 20 deg.C. After 5 days, the infection of the tomato plants was determined.
The assessment data obtained were converted to percent infection. 0~ denoted no infection and 100% denoted that the plants were totally infected.
In this test, for example, the following compounds exhibited a very good action which was significantly superior to that of the compound (B) known from the prior art: compounds (12), (1), (2), (8) and (10).
Preparative Examples 15 E~xa~ple 1 C2 H5 ,~, C~3 I H - C - OCH3 ( 1 ) o Process variant (a) 13.3 g (0.122 mol) of methoxyacetyl chloride were added dropwise to a solution of 18.4 g (0.0816 mol) of 20 N-(2,6-xylyl)-ethylglycine methyl ester and a few drops of dimethylformamide in 80 ml of toluene at room tempera-ture and the mixture was stirred at 80 C for 3 hours.
After cooling, the solution was diluted with ethyl acetate, washed wi~h dilute hydrochloric acid, water and sodium 25 bicarbonate solution, dried over sodium sulphate and evaporated.
The residue was crystallised from ligroin. 10.4 g (43.5%
of theory) of N-methoxyacetyl-N-(2~6-xylyl)-ethylglycine methyl ester of melting point 96~97C were obtained~
.

CH3 ~2H~
~ ~ CH - 8 O~H3 ~u H
.,..~

Le A 19 573 3~2 A mixture Or 3~7.3 g ~2,l.mol) o~ 2~b.romobutyric acid methyl eæter, 127.0 g (1.05 mol) o~ 2',6-xylidine, 121 8 g (2.1 mol) of potassium fluoride and 100 ml of dimethylformamide was stirred at 100C under nitrogen for 39 hours. After cooling, it was filtered, the filtrate was poured into water, the oil which had separated out was extracted with methylene chloride and the extract was washed with water J dried over sodium sulphate and evaporated The residue was fractionated over a column, in vac'uo. 112.0 g (48.3% of theory) of N-(2,6-xylyl)-ethylglycine methyl ester o~ boiling point 100-110C/0.9 mbar were obtained.
E~ample 2 2Hg f1 N/ 3 (2) Process variant (a?
18.4 g of pyrazol-l-yl-acetyl chloride hydrochloride (prepared from 0.1 mol of pyrazol-l-yl-acetic acid~
were introduced into a solution, boiling under reflux, of 11.1 g (0.05 mol) of N-(2,6~xylyl)-ethylglycine methyl ester, 7.9 g (0.1 mol) of pyridine and 1.2 g (0.01 mol) of 4-dimethylaminopyridine in the cour~e o~ 35 minutes and the mixture was heated under reflux for 22 hours. The reaction mixture was evaporated in va~uo, the residue was partitioned between ethyl acetate and 1 molar citric acid and the or~anic pha~e was washed with 5 strength sodium hydroxide solution and water, dried over sodium sulphate and concentrated.. The res.idue wa crystalliæed from to.luene/petroleum ether (1:4). 11.3 g (68.7~ ~ theory) of N-(pyrazol-l-yl-acetyl)-N~(2,6-xylyl)-ethylglycine methyl ester of.me.lting point 113~115C were obtained.

Le A 19 573 ., 5~34Z

P~e'pa'~ ~
.

Cl - C - CH2 - N J x HCl ~N

One drop of dimethylformamide was added to a sus-pension of 12.6 g (0.1 mol) of pyrazol-l-yl-acetic acid in 40 ml of toluene, and 19.05 g (0.15 mol) of oxalyl chloride were added dropwise at 25-30~ (cooling with ice).
After stirring the mixture at room temperature for 17 hours, it was filtered and the residue was boiled down twice with toluene. 18.4 g of crude pyrazol-l-yl-acetyl chloride hydrochloride, which could be employed further without purification, were obtained.
Example 3 CH~ C - CH2 - OH
O ..

Proc-ess variant (f) .
A solution of 21.3 g (0,38 mol) of powdered potassium hydroxide in 200 ml of methanol was added dropwise to a solution of 61.1 g (0.19 mol) of N-acetoxyacetyl-N-(2,6-xylyl)-ethylglycine methyl ester in 200 ml of methanol at room temperature in the course of 15 minutes and the mixture was stirred at room temperature for 1 hour and at 50C for 3.5 hours. The reaction solution was evaporated, the aqueous solution of the residue was ex-tracted by shaking with ether and the product phase was acidified with half-concentrated hydrochloric acid and extrac~d with ethyl acetate. The extract was dried over sodium sulphate and evaporated.

Le' A 19 573 The residue was dissolved in 180 ml of methanol àn~3 after adding 81.0 g (0.571 mol) of boron trifluoride etherate (48% strength), the mixture was heated under reflux for 17 hours. The reaction solution was poured into 1,000 Ir.l of 10% strength sodium bicarbonate solution, whilst cooling with ice, the mixture was extracted several times with methylene chloride and the extract was washed with water, dried over sodium sulphate and evaporated.
48 1 g (90.6% of theory) of N-hydroxyacetyl-N-(2,6-xylyl)-10 ethylglycine methyl ester of melting point 101-102C were obtained .
- Example 4 . . _ .

(~--N\ (4) CH3 ,C, - CH2 ~ 0 - S02 - CH3 Process variant (e)(l) 11.5 g (0.1 mol) of methanesulphonic acid chloride were added dropwise to a solution of 13.95 g (0.05 mol) of N-hydroxyacetyl-N-(2,6-xylyl)-ethylglycine methyl ester (Example 3) and 12.3 g (0.11 mol) of 1,4-diazabicyclo[2,2,2]-octane in 150 ml of methylene chloride at 20-25C (cooling 20 with ice) and the mixture was stirred at room temperature for 17 hours. The reaction solution was washed with water, with 10% strength aqueous pyridine, with dilute hydrochloric acid and with water, dried over sodium sulphate and evaporated. The residue was crystallised from ligroin/
25 toluene (7:2). 13~9 g (78~8% of theory) of N-methane-sulphonyloxyacetyl-N-(2,6-xylyl)-ethylglycine methyl ester of melting point 92C were obtained.
Examp le 5 , . .
CH Cl -OCH

CH3 ~CI - CH2 _ o _ O O
Process variant (e)(2) Le A 19 573 34~

4 ml of 1 molar ethereal hydrogen chloride were added to a l~ixture of 11.2 g (0.04 mol) of N-hydroxyacetyl-N-(2,6-xylyl~-ethylglycine methyl ester (Example 3) and 13.8 g (0.16 mol) of 3,4-dihydro-2H-pyrane, and the mixture ~,7as stirred at room temperature for 23 hours. After dilution with ethyl acetate, the mixture was washed with sodium bicarbcnate solution and water, dried over sodium sulphate and evaporated and the oily residue was freed from volatile impurities using an oil pump. 14.4 g (99.2~ of theory) of N-tetrahydro-pyranyloxyacetyl-N-(2,6-xylyl)-ethylglycine methyl ester were obtained as an oil with the refractive index nD = 1.4959.
The follcwing ccmpounds of the general formula :

R2 Rl IC2H5 11 ~ ~ CH - C - Y - R
R3~ ~ \ C R4 (I) were obtained in an analogous manner.

o~
- ~ o ~ ~ ~ a ~, a a~ , a O

~; ~
~ o o o o o o o o o ~ ~ Z~
~o ~ r ~~7 ~

~; P~ X

~ ~: X

.,~

Claims

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. N,N-Disubstituted ethylglycine (thiol)esters of the general formula I

in which R represents alkyl, hydroxyalkyl, cyanoalkyl, alkenyl, alkynyl, halo-genoalkyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, acyloxy-alkyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl, dialkylamino-alkyl or aralkyl optionally substituted by one or more substituents selected from halogens, cyano, nitro, alkyl with 1 or 2 carbon atoms or halogenoalkyl with 1 or 2 carbon atoms and up to three identical or different halogen atoms;
R1 represents hydrogen, alkyl, alkoxy or halogen; R2 represents hydrogen, alkyl, alkoxy or halogen; R3 represents hydrogen or alkyl; Y represents oxygen or sulphur and R4 represents furyl, tetrahydrofuryl, thienyl or tetrahydrothienyl;
isoxazolyl which is optionally substituted by alkyl; hydroxyalkyl; alkyl, alkenyl or alkynyl which is optionally substituted by cyano or thiocyano; cyclo-alkyl; dihalogenoalkyl; or the grouping -CH2-Az, -CH2OR5, -CH2-SR5, -OR5, -SR5, -CH2-OSO2R5, -CH20COR5 or wherein R5 represents an alkyl, alkenyl, alkynyl, which alkyl, alkenyl or alkynyl group is optionally substituted by halogen, cyano or thiocyano, or an alkoxyalkyl group and Az represents pyrazol-1-yl, 1,2,4-triazol-1-yl or imidazol-1-yl.

2. Compounds according to claim 1, characterised in that R represents straight-chain or branched alkyl with l to 6 carbon atoms; hydroxyalkyl or cyanoalkyl with in either case 1 to 4 carbon atoms in the alkyl part;
alkenyl or alkynyl with 2 to 4 carbon atoms; halogenoalkyl with 1 to 4 carbon atoms and up to 5 halogen atoms;
cycloalkyl with 3 to 7 carbon atoms; cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part and 1 to 4 carbon atoms in the alkyl part; alkoxyalkyl, alkoxy-alkoxyalkyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl or dialkylaminoalkyl with 1 to 4 carbon atoms in each alkyl part; acyloxyalkyl with 1 to 4 carbon atoms in the alkyl part, the acyl part having the general formula R7-CO- wherein R7 denotes alkyl with 1 to 4 carbon atoms, halogenoalkyl with 1 to 4 carbon atoms and up to 5 halogen atoms or aryl with 6 to 10 carbon atoms or aralkyl with 6 to 10 carbon atoms in the aryl part and 1 to 4 carbon atoms in the alkyl part, the aryl radical or the aryl part of the aralkyl radical optionally carrying one or more substituents selected from halogen, cyano, nitro, alkyl with 1 to 2 carbon atoms and halogenoalkyl with up to two carbon atoms and up to 3 identical or different halogen atoms; or aralkyl which has 6 to 10 carbon atoms in the aryl part and l to 4 carbon atoms in the alkyl part, the aryl part optionally carrying one or more substituents selected from halogen, cyano, nitro, alkyl with 1 or 2 carbon atoms and halogenoalkyl with up to 2 carbon atoms and up to 3 identical or different halogen atoms, R1 and R2 are identical or different and each represent hydrogen, straight-chain or branched alkyl or alkoxy with 1 to 4 carbon atoms or halogen, R3 represents hydrogen or straight-chain or branched alkyl with 1 to 4 carbon atoms, Y represents oxygen or sulphur, R4 represents furyl, tetrahydrofuryl, thienyl or tetrahydrothienyl; isoxazolyl which is optionally substituted by methyl or ethyl; hydroxyalkyl with Le A 19 573 1 to 2 carbon atoms; alkyl with 1 to 4 carbon atoms, optionally substituted by cyano or thiocyano; alkenyl or alkynyl with in either case 2 to 4 carbon atoms, optionally substituted by cyano or thiocyano; cycloalkyl with 3 to 7 carbon atoms; dihalogenoalkyl with 1 to 2 carbon atoms; or the grouping -CH2-Az, -CH2-OR5, -CH2-SR5, -OR5, -SR5, -CH2-OSO2R5,-CH2OCOR5 or, Az represents pyrazol-1-yl, 1,2,4-triazol-1-yl or imidazol-1-yl, and R5 represents alkyl with 1 to 4 carbon atoms or alkenyl or alkynyl with in each case 2 to 4 carbon atoms, in each case optionally substituted by halogen, cyano or thiocyano, or represents alkoxyalkyl with 1 to 4 carbon atoms in each alkyl part.

3. N-Methoxyacetyl-N-(2,6-xylyl)-ethylglycine methyl ester of the formula

4. N-(Pyrazol-1-yl-acetyl)-N-(2,6-xylyl)-ethylglycine methyl ester of the formula

5. N-Acetoxyacetyl-N-(2,6-xylyl)ethylglycine methyl ester of the formula

6. N-(1,2,4-Triazol-1-yl-acetyl)-N-(2,6-xylyl)-ethylglycine methyl ester of the formula .

7. N-Furoyl-N-(2,6-xylyl)-ethylglycine methyl ester of the formula

8. A method of combating fungi which comprises applying to the fungi, or to a habitat thereof, a fungicidally effective amount of a compound according to claim 1.

9. A method according to claim 8 wherein the compound is used in the form of a composition containing said compound as active ingredient in ad-mixture with a diluent or carrier.

10. A method according to claim 9 in which a composition is used containing from 0.0001 to 1% of said compound, by weight.

11. A method according to claim 9 in which a composition is used containing from 0.001 to 0.5% of said compound by weight.

12. A method according to claim 8, 9 or 11,in which said compound is applied to soil in an amount of 0.00001 to 0.1% by weight.

13. A method according to claim 8, 9 or 11,in which said compound is applied to soil in an amount of 0.0001 to 0.02% by weight.

14. A method according to claim 8, 9 or 11,in which said compound is applied to seed in an amount of 0.001 to 50 g per kg of seed.

15. A method according to claim 8, 9 or 11,in which said compound is applied to seed in an amount of 0.01 to 10 g per kg of seed.

16. The method according to claim 8, 9 or 11, in which said compound is N-methoxyacetyl-N-(2,6-xylyl)-ethylglycine methyl ester.

17. The method according to claim 8, 9 or 11, in which said compound is N-(pyrazol-1-yl-acetyl)-N-(2,6-xylyl)-ethylglycine methyl ester.

18. The method according to claim 8, 9 or 11, in which said compound is N-(acetoxyacetyl-N-(2,6-xylyl)-ethylglycine methyl ester

19. The method according to claim 8, 9 or 11, in which said compound is N-(1,2,4-triazol-1-yl-acetyl)-N-(2,6-xylyl)-ethylglycine methyl ester.

20. The method according to claim 8, 9 or 11, in which said compound is N-furoyl-N-(2,6-xylyl)-ethylglycine methyl ester.