DD150420A5 - FUNGICIDAL AGENTS - Google Patents

Abstract

The invention relates to fungicidal agents which are novel N, N-disubstituted ethylglycine (thiol) esters of general formula I in which R, R & exp1 !, R & exp2 !, R & exp3 !, R & exp4! and Y have the meaning given in the description as active ingredients. These agents are suitable for use as pesticides and can be used to combat Oomycetes with particular success.

Description

The present invention relates to fungicidal compositions containing new Ν, Ν-disubstituted ethyl glycine (thiol) esters as active ingredients.

Characteristic of the known technical solutions

It has already been disclosed that haloacetanilides, such as, for example, N-chloroacetyl-N- (2,6-dialkylphenyl) -alanine or glycine-alkyl esters, can be used successfully for combating fungal plant diseases (compare DE-OS 2 350 944 and US Pat. No. 3,780,090). However, their effect is not always very satisfactory, especially at low application rates and concentrations, especially in the control of Phytophthora species. "

Object of the invention

Surprisingly, the N, N-disubstituted ethyl glycine (thiol) esters according to the invention exhibit a considerably higher activity, in particular against Phytophthora, than the N-chloroacetyl-N- (2,6-diaikylphenyl) alanine known from the prior art or glycine alkyl esters, which are chemically and functionally obvious compounds. The active compounds according to the invention thus represent an enrichment of the art.

56 991 11

Explanation of the essence of the invention

There were new N, U-disubstituted ethyl glycine (thiol) ester of the general formula

CH-C-Y-R

in which

R is alkyl, hydroxyalkyl, cyanoalkyl, alkenyl, alkynyl, haloalkyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, acyloxyalkyl, alkylthioalkyl, alkylsulfinylalkyl, alkylsulfonylalkyl, dialkylaminoalkyl or optionally substituted aralkyl,

R is hydrogen, alkyl, alkoxy or halogen,

R is hydrogen, alkyl, alkoxy or halogen,

R · is hydrogen or alkyl, Y is oxygen or sulfur,

R 1 is furyl, tetrahydrofuryl, thienyl, tetrahydrothienyl; optionally substituted by alkyl isoazolyl; Hydroxyalkyl, optionally cyano- or thiocyano-substituted alkyl, alkenyl and alkynyl; cycloalkyl; dihaloalkyl; and the moieties -CH ₂ -Az, -CH ₂ - -OR ⁵ , -CH ₂ -SR ⁵ , -OR ⁵ , -SR ⁵ , -CH ₂ -OSO ₂ R ⁵ , -CH ⁵

and r-CHp-O- · - ^^), where

10.12.1980 20358 -3- 56 991/11

R is optionally substituted alkyl, alkenyl, alkynyl and alkoxyalkyl, and

Az is pyrazol-1-yl, 1,2,4-triazole, and imidazol-1-yl,

found.

Furthermore, it has been found that the N, N-disubstituted ethylglycine (thiol) ester of the formula (I) is obtained when

a) N-phenyl-.ethylglycine (thiol) ester of the formula

C ₂ H 0

CH-C-Y-R

(II)

in which

1 2 R, R, R,

R and Y are as defined above.

with acid chlorides or bromides or anhydrides of the formulas

R ⁴ - C - Cl (Br) (HIa)

or.

(R ⁴ .- 'C -) ₂ O (HIb),

10.12.1980 22 0 35 8 - 4 - 56 991/11

in which

R has the meaning given above,

in the presence of a diluent and optionally

in the presence of an acid binder,

b) N-acyl-N-phenyl-ethylglycines of the formula

R ² . C ₂ H »S -C- 0 - H ~ <Γ- Il O R ⁴ in which 1 2 3 K g K ₉ K and R ⁴ the above a naeaet those E

with alcohols or, thiols of the formula

R-Y-H (V),

in which

R and Y are as defined above,

in the presence of a condensing agent and optionally

in the presence of a diluent,

c) N-acyl-N-phenyl-ethylglycine chlorides of the formula

12/10/1980

0 35 8 - 5 - - 56 991/11

^C 2 ^H 5 °

CH- Cl-

(VI)

CR ⁴

in which * ²

R ¹ , R ² , R ³ and R have the abovementioned meaning,

with alcohols or thiols of the formula (V) in the presence of a diluent and optionally in the presence of a ftT base; or individual compounds of the formula (I) ₁ by

d) N-haloacetyl-N-phenyl-ethylglycine (thiol) ester äer formula

CU O

2 oil I ^D Il

.CH-C-Y-R N ^ (VII),

C ~ CH ₀ - shark

if ^

in which

R and Y are as defined above and --Hai is chlorine, bromine or iodine

with compounds of the formula

B-X (VIII),

in which

10.12.1980 220358 -6- 56 991/11

X for Az, Cyano, Thiocyano and the grouping

5 5 -OR or -SR or alkylcarbonyloxy with 1

to 4 carbon atoms in the alkyl moiety and B is hydrogen or an alkali metal,

in the presence of a diluent and optionally in the presence of an acid binder, or

e) N-hydroxyacetyl-N-phenyl-ethylglycine (thiol) esters of the formula according to the invention

^C 2 ^H 5 O Y-R R ¹ I Il ^ CH.- C - ~ OH - Ν " C - Il CH ₂

in which

R and Y are as defined above,

(1) optionally after activation by means of alkali metal with halides aer formula

Shark - R ⁶ (X),

in which

Hai has the meaning given above, and "

R is the radical R ° and the groups -SO ₂ R and -COR, where

R has the meaning given above,

56 991 11

in the presence of a diluent and optionally in the presence of an acid binder, or

(2) with denydropyran of the formula

(XI)

in the presence of a diluent and optionally in the presence of a catalyst.

In addition, it has been found that the new N, H-disubstituted ethylglycine (thiol) esters of the formula (I) have strong fungicidal properties.

The Ν, ϊΤ-disubstituted ethylglycine (thiol) esters according to the invention are generally defined by formula (I). In this formula, R preferably represents straight-chain or branched alkyl having 1 to 6 carbon atoms; for hydroxy and cyanoalkyl each having 1 to 4 carbon atoms in the alkyl moiety; for alkenyl and alkynyl with

12/10/1980

2203 58 -8- 56 991/11

Carbon atoms and haloalkyl having 1 to 4 carbon and up to 5 halogen atoms, in particular having up to 2 carbon and up to 3 identical or different halogen atoms, wherein as halogens in particular fluorine and chlorine are »R_ is furthermore preferably cycloalkyl and cycloalkylalkyl 3 to 7 carbon atoms in each cycloalkyl part and 1 to 4 carbon atoms in the alkyl part; for alkoxyalkyl, alkoxyalkoxyalkyl, alkylthioalkyl, alkylsulf inylalkyl, alkylsulfonylalkyl and dialkylaminoalkyl having 1 to 4 carbon atoms in each alkyl moiety, and preferably for acyloxyalkyl having 1 to 4 carbon atoms in the alkyl moiety, wherein in the acyl moiety of the general formula R -CO- the moiety F? preferably means:

Alkyl of 1 to 4 carbon atoms; Haloalkyl having 1 to 4 carbon and up to 5 halogen atoms, in particular having up to 2 carbon and up to 3 identical or different halogen atoms, halogens being in particular fluorine and chlorine; and optionally in the aryl part substituted aryl or arylalkyl having 6 to 10 carbon atoms in the aryl moiety and 1 to 4 carbon atoms in the alkyl moiety, in particular phenyl or benzyl, preferably as substituents in Frag © come: halogen, in particular fluorine, chlorine and bromine; Cyano, nitro, alkyl having 1 to 2 carbon atoms and haloalkyl having up to 2 carbon and up to 3 identical or different halogen atoms, halogens being in particular fluorine or chlorine, by way of example trifluoromethyl. In addition, R preferably represents aryl moiety which is optionally substituted in the aryl moiety and has 6 to 10 carbon atoms in the aryl moiety, in particular phenyl, and 1 to 4 carbon atoms in the alkyl moiety, preference being given to substituents: halogens, in particular fluorine, chlorine and bromine; Cyano, nitro, alkyl having 1 to 2 carbon atoms and haloalkyl with

10.12.1980 2 2 0 3 5 8 - 9 - 56 991/11

up to 2 carbon atoms and up to 3 identical or different halogen atoms, halogens being in particular fluorine and chlorine, by way of example trifluoromethyl being mentioned,

1 2 JR and. F? are preferably hydrogen, straight-chain or branched alkyl or alkoxy having 1 to 4 carbon atoms and halogen, in particular fluorine, chlorine or bromine, JR is preferably hydrogen and straight-chain or branched alkyl having 1 to 4 carbon atoms. Y is preferably oxygen or sulfur. R, is preferably furyl, tetrahydrofuryl, thionyl, tetrahydrothienyl, optionally substituted by methyl or ethyl isoxazolyl, hydroxyalkyl having 1 to 2 carbon atoms, optionally substituted by cyano or thiocyano-substituted alkyl with 1 to 4 and alkenyl and alkynyl each having 2 to 4 carbon atoms and cycloalkyl of 3 to 7 carbon atoms; furthermore preferably for dihaloalkyl having 1 to 2 carbon atoms, fluorine and chlorine preferably being mentioned as the halogen atoms, and also the groups -CHp-Az, -CH ₂ -OR, -CH ₂ -SR ⁵ , -OR ⁵ , -SR ⁵ , -CH ₂ -OSO ₂ R ⁵ , -CHgOCOR ⁵ and -CHg-O

A Z ₁ is preferably pyrazol-1-yl, 1,2,4-triazol-1-yl and imidazol-1-yl. Preferably, JR is alkyl optionally substituted by halo, especially fluoro, chloro and bromo, cyano and thiocyano, having 1 to 4 and alkenyl and alkynyl each having 2 to 4 carbon atoms and alkoxyalkyl having 1 to 4 carbon atoms in each

SH

Alkyl part.

Very particular preference is given to those compounds of the formula (I) in which _R is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, hydroxyethyl, cyanomethyl, allyl, propargyl, Chloroethyl, cyclopropyl,

10 * 12.1980 220358 -ίο »56 991/11

Cyclopropylmethyl, cyclohexyl, cyclohexylmethyl, methoxyethyl, ethoxyethyl, methylthioethyl, ethylthioethyl, methoxyethoxyethyl, chloroacetoxyethyl, methylsulfinylethyl, ethylsulfinylethyl, methylsulfonylethyl, ethylsulfonylethyl, benzyl optionally substituted by chlorine, methyl and / or ethyl, and also dimethylaminoethyl or di-methyl

12 3

ethylaminoethyl; f? _# JR and FJ are the same or different and are hydrogen, methyl, ethyl, n -propyl, isopropyl, η-butyl, isobutyl, sec-butyl or tert-butyl

1 2 stand; R and JR 'are also methoxy, ethoxy, isopropoxy, fluorine, chlorine or bromine; Y has the meaning given in the definition of the invention; and F? 2-furyl, 2-thienyl, 2-tetrahydrofuryl, 5-methylisoxazole-3-yl, methoxymethyl, ethoxymethyl, Allylox _v, methyl, propargyloxymethyl, ethoxymethoxymethyl, Methylmercaptomethyl, methoxy, ethoxy, methylmercapto, cyclohexyl, dichloromethyl, HyxJroxyrnethyl, methanesulfonyloxymethyl, Acetoxymethyl, propionyloxymethyl, dichloromethyl, pyrazol-1-yl-methyl, imidazol-1-yl-methyl, 1,2,4-triazol-1-yl-methyl and tetrahydropyran-2-yl-oxymethyl. ,

Specifically, other than those described in the preparation examples, the following compounds of the general ^F Ormel (I) include:

CH-C-Y-R

(I)

0 35

- ii -.

10.12.1980 56 991/11

H H H '.H H H H H H H H H H H H H H H H H H H H H H H H H H H

H H H H H H H H H H H H H

^ o ^

O O O O O O O O O O O O

CH.

• ^C 2 ^H 5 .CHgCHgCl .CH ₂ CHgOCH ₃ .CHgCHgOCgH ₄ OCH ₃ .CHgCHgOCOCHgCl .CHg-CH = CHg CHg- CS (

-CHg - (H .CHGCHgSCH .CHgCHgCHoCH .CHgCHggOngCH ₃ .CHgCHg-f

-CH ₂ Cl

.CH ₂ CN

.cl

10.12.1980 56 991/11

CH, 6-CH.

CH- 6 »CH.

CH, 6-CH.

6-CH.

CH, 6-CH.

CH, 6-CH.

CH, 6-CH.

CH, 6-CH.

CH, 6-CH.

CH, 6-CH.

CH, 6-CH.

CH, 6-CH.

CH, 6-CH.

CH, 6-CH.

CH, 6-CH.

H H H H H H H H H H H H

O'

• Π

^ O ^

0 '

ί ι

^s 0 "

-C ₂ H ₅

ο ο ο ο ο

OCH

-CH ₂ CH ₂ OCOCH Cl

-CH ₂ -CH = CH ₂

-CH ₂ - (H

-CH ₂ CH ₂ SCH ₃ -CH ₂ CH ₂ SOCH -CH ₂ CH ₂ SO ₂ CH ₃

-NCCH ₃ ) ₂

-CH ₂ -

Cl '

-CH ₂ CN

10.12.1980 56 991/11

^CH 3 6-C ₂ H ₅ H ^CH 3 6-C ₂ H ₅ H ^CH 3 6-C ₂ H ₅ H ^CH 3 6-C ₂ H ₅ H ^CH 3 6-C ₂ H ₅ H ^CH 3 6-C ₂ H ₅ H ^CH 3 6-C ₂ H ₅ H CH ₃ 6-C ₂ H ₅ H CH ₃ 6-C ₂ H ₅ H ^CH 3 6-C ₂ H ₅ H CH, 6-C ₂ H ₅ H CH ₃ 6-C ₂ H ₅ H ^CH 3 6-C ₂ H ₅ H CH ₃ 6-C ₂ H ₅ H ^CH 3 6-C ₂ H H

I i

CH

O -CH ₃ O - ^C 2 ^H 5 O. -CH ₂ CH ₂ Cl O -CH ₂ CH ₂ OCH ₃ O -CH ₂ CH ₂ OC ₂ H ₄ OCH ₃ O -CH ₂ CH ₂ OCOCh ₂ Cl O -CH ₂ -CH = CH ₂ O -CH ₂ -C =CH O \ ^H / O -CH ₂ - / 7Γ \ O - CH ₂ CH ₂ SCH O "* 2 2 3 O -CH ₂ CH ₂ SO ₂ CH ₃ O - CH ₂ CH ₂ -N (CH ₃ ) ₂ O V / X O -CH ₂ CN

22035

10 * 12.1980 56 991/11

, 4

H H H -CH ₂ -O-CH ₃ O H H H -Chg-O-CH O H H H -Chg-O-CH O H H H -Chg-O-CH O H H H -Chg-O-CH O H H H. -CHg-O-CH ₃ O H H H -CHg-O-CH · O H H .H -CH ₂ -O-CH ₃ O H H H -C'Hg-O-CH • o H H H -CH ₂ -O-CH ₃ O H H H -CH ₂ -O-CH ₃ O H H H -CH ₀ -O-CH- O H H H -Chg-O-CH Ό H H H -CH ₂ -O-CH ₃ O H H H -Chg-O-CH O H H H -Chg-O-CH O

CH.

• ^C 2 ^H 5 .CHgCHgCl .CH ₂ CHgOCH ₃ .CH ₂ CHgOCgH ₄ OCH ₃ • CH ₂ CHgOCOCHgCl .CHg-CH = CH ₂

-( H

-CH ₀ CHp SCH.,

-CH ₀ CH ₀ SOCH, 2 2

-CHgCHgSO ₂ CH ₃ -CH ₂ CH ₂ -N (CH ₃ ;

Cl

• CHgCN

220358

10.12.1980 56 991/11

, CH_ 6-CH.

3 ^

CH ₃ 6-CH,

CH 6-CH,

CH ₃ 6-CH.

CH-6-CH.

3 ^

CH, 6-CH.

CH, 6-CH.

CH, 6-CH.

CH, 6-CH.

CH, 6-CH.

CH ₃ 6-CH, CH, 6-CH,

CH, 6-CH.

CH, 6-CH.

CH 6-CH

H -CHg-O-CH ₃ 0 H -Chg-O-CH 0 H -CH ₀ -O-CH, C.O 0 H -CHg-O-CH ₃ 0 H -CHg-O-CH ₃ 0 H -CHg-O-CH ₃ 0 H -CHg-O-CH ₃ 0 H -CHg-O-CH ₃ 0 H -Chg-O-CH 0 H -CHg-O-CH ₃ 0 H -Chg-O-CH 0 H -Chg-O-CH 0 H -CHg-O-CH ₃ H -CH ₂ -O-CH ₃ 0

^C 2 H 5 Cl CH CH 2 CH ₂ OCH ₃ CH 2 Chg OC ₂ H ₄ OCH ₃ CH 2 Chg OCOCHgCl CH 2 Chg -CH = CHg CH 2 -CH CH 2

- <H

H-CHG-O-CH

Chg Chg CN SCH 3 ^CH 3 Chg Chg SOCH ₃ ^CH 3 Chg Chg Suction __C1 ^CH 2 Chg -N ( Chg ^mm / t Cl ^ Chg

10 * 12.1980 55 991/11

^CH 3 6-C ₂ H ₅ H -CH ₂ -O-CH O CH ₃ 6-C ₂ H ₅ H -Chg-O-CH O ^CH 3 6-C ₂ H ₅ H -Chg-O-CH O ^CH 3 6-C ₂ H ₅ H -CHg-O-CH ₃ O ^CH 3 6-C ₂ H ₅ H -CHg-O-CH ₃ O CH ₃ 6-C ₂ Hg H -CH ₀ -O-CH, O ^CH 3 6-C ₂ H ₅ H -Chg-O-CH O CH ₃ 6-C ₂ H ₅ H -Chg-O-CH O ^CH 3 6-C ₂ H ₅ ' H -CHg-O-CH ₃ O ^CH 3 6-C ₂ H ₅ H "CHG-O-CH O CH ₃ 6-CgHg H -Chg-O-CH O ^CH 3 6-C ₂ H ₅ H -CHg-O-CH ₃ O CH ₃ 6-CgHg H -Chg-O-CH O ^CH 3 6-CgHg H -CHg-O-CH ₃ O ^CH 3 6-CgH ₅ H -CH ₂ -O-CH ₃ O CH ₃ 6-C ₂ H ₅ H -Chg-O-CH O

CH.

ro " H 5 Cl 3 CH 2 OCH ₇ CH 2 Chg OCH ^H 4 ₂ ci CH 2 Chg OC ₂ OCOCH CH 2 CH ₂ -CH = CH CH 2 Chg P * - CH 2 CH 2

CHG ~ ( H

CHgCHgSCH ₃ CHgCH ₂ SOCH ₃ CHgCH ₂ SO ₂ CH ₃

"CHgCN

I O

PO *

PO

PO i

PO

ro

ώόόό όόώώώώό

ο.

ι I I 1 O O O O X X X X PO PO PO PO O O O X X I PO PO PO (S) O 8th O I X PO O X O X OJ

I I I I I I I O O O O O ο ' O X X X X X X PO PO PO PO PO PO X I I O O O O ul O O X , X X "ι X ro PO ro PO O Il O O O O X O O O O 1-' X O PO X PO O X W X PO O O O   X

70

70 PO

70 O *

UI 1 · *

cn ο *

O PO

H> CD

R ¹ R ²

10.12.1980 56 991/11

H H

H H

H H

CH, 6-CH_ 3 3

CH ₃ 6-CH ₃

CH ₃ 6-CH ₃

H-CH,

-γ / Π

-CH ₂ -

H -CH ₂ -Γ

6-CH ₃ H -CH ₂

-ι / = 1

VPJ

^Η - ⁰ Vw

H-CH,

-Q

CH, 6-CHL H -CH

² " ^Ν 3

- ^CH 2 Cl

H-CH,

-CH ₂ CH ₂ -NCCH ₃ ) ₂ Cl

CH ₂ CN

CH ₀ CH ₀ OC ₀ H.0CH

C, έ. C.Q.

CH ₂ -CH = CH ₂

CH ₃ 6 -CH ₃ H -CH ₂ -Γ

CH ₂ -C = CH

CH, 6-CH-H-CH ₀ -N

CH 6 -CH H -CH ₀ -ί

Wό Cm

CH-6-CH-H-CH ₀ ...

^{ό ό} *Κι =¹

-α

O-CH ₂ ~ ( H

CH ₂ CH ₂ SCH

220 358 - 19 - Y 10 _e 12.19S0 R ² R ³ R ⁴ O 56 991/11 R ¹ 6-CH ₃ H -Chg "V O R CH ₃ 6-CH ₃ H -Chg -Q O -CHGCH ₂ SOCH ₃ CH ₃ 6-CH ₃ H -Chg -Q O ¹ -CHGCH ₂ SOgCH ₃ ^CH 3 6-CH ₃ H -Chg O -CHgCHg-N (CH ₃ ) g ^CH 3 6-CH ₃ H -Chg -a N = - ' O ^CH 3 6-CgHg H -Chg O -CHgCN ^CH 3 6-C ₂ Hg H -Chg -C] -CH ₃ CH ₃ 6-C "H_ c. b H -Chg O - ^C 2 ^H 5 CH ₃ 6-CgHg H -Chg "V O -CHgCHgCl ^CH 3 6-CgHg H -Chg -N ~ " O -CHgCHgOCH ₇ CH ₃ 6-CgH ₅ H -Chg -N ⁰ -CHgCHgOCgH ₄ OCH ^CH 3 6-CgHg H -Chg -5 O -CHgCHgOCOCHgCl CH ₃ 6-CgHg H -Chg  Ή -Chg-CH = CHg ^CH 3 -Chg-ČSCH

22.0358

10.12.1980 56 991/11

R ¹ R ²

, 4

CH_ 6-C ₀ H ₁ . H-CH,

CH, 6-C _o H _c H -CH _r

-Cl

-CH

^0Η 3 6-C ₂ H ₅ H -CHg ~ f O -CH ₀ CHgSCH ^CH 3 6-C ₂ H ₅ H O -CH ₂ CH ₂ SOCH ₃ ^CH 3 6-C ₂ H ₅ H P = -CHg -N ! ° -CH ₂ CHgSOgCH ₃ CH ₃ 6-C ₂ H ₅ H -CH ₂ -N 0 -CHgCHg-N (CH ₃ ) g ^CH 3 6-C ₂ H ₅ H -CHg ~ {C \ - Cl -CH ₂ -t 0 Cl ^CH 3 6-C ₂ H ₅ H 0 -CHgCN H H H A 0 -CH ₃ H H H / - ' 0 H H H | \ L ~ 0 -CH ₂ CH ₂ OCH ₃ H H H -CH ₀ -N ~ " ^Δ Vi = 0 -Chg-CH = CHg H H H -CHClg 0 -Chg-CHCH H H H -CHClg 0 -CHgCHgOC ₂ H ₅ H H H -CHClg 0 - ^C 2 ^H 4 ^0C 2 ^H 4 ^0CH 3 H H H -CHClg 0 -CHgCN ^CH 3 6-CH, H -CHClg 0 -C ₂ H ₅ ^CH 3 6-CH ₃ H -CHClg -CH ₂ CH ₂ OCH, -CHClg -CHClg -CHClg -CHClg

220358

10.12.1980 56 991/11

^CH 3 6-CH ₃ H -CHCIg O -Chg-CH = CHg ^CH 3 6-CH3 H '-CHCIg O -Chg-CHCH ^CH 3 6-CH3 H -CHCIg O -CHgCHgOCgHg ^CH 3 6 ~ CH H -CHCIg O -C ₂ H ₄ OC ₂ H ₄ OCH ₃ ^CH 3 6-CH3 H -CHCIg O -CHgCN ^CH 3 6-CgHg H -CHCIg O -CH ₃ ^CH 3 6-CgHg H -CHCIg O -CgH ₅ ^CH 3 6-CgHg H -CHCIg O -CHgCHgOCH ₃ ^CH 3 6-CgH ₅ H ' -CHCIg O -Chg-CH = CHg ^ce v 6-CgH ₅ H -CHCIg O · »CHp-C = CH CH ₃ 6-CgH ₅ H -CHCIg O -C ₂ H ₄ OC ₂ H ₅ ^CH 3 6-CgHg H -CHCl ₂ O -CgH OCgH OCH ^CH 3 6-C ₂ Hg H -CHCIg O -CHgCN H H H -CHgOCOCH - O -CH ₃ H H H -CHgOCOCH O - ^C 2 ^H 5 H H H -CHgOCOCH 0 -CHgCHgOCH ₃ H H H -CHgOCOCH O -CHg-CH-CH ₂ H H H -CHgOCOCH O -Chg-C = CH H H H -CHgOCOCH ₃ O -CgH ₄ OC ₂ H ₄ OCH ₃ H ~ H H -CHgOCOCH ₃ O -CHgCN ^CH 3 6-C ₂ H ₅ H -CH ₀ -OCOCH ^ 3 O -CH ₃ ^CH 3 6-CgHg H -CHg-OCOCH ₃ O - ^C 2 ^H 5 ^CH 3 6-CgHg H -CHg-OCOCH ₃ O -CHgCHgOCH ₃

, 4

10.12.1980 56 991/11

CH ₃ 6-CgHg H -Chg-OCOCH J J 0 -Chg-CH = CH ₂ ^CH 3 6-CgH ₅ H '-CHg-OCOCH ₃ -CH ₉ -N ~ I 0 -CH ₂ -C =CH CH ₃ 6-CgH ₅ H -CH ₂ -OCOCH ₃ 0 -CHgCHgOC ₂ Hg ^CH 3 6-CgHg H -CH ₂ -OCOCH - ^CH 2 "C 0 -C ₂ H ₄ OC ₂ H ₄ OCH ₃ ^CH 3 6-CgHg H -CHg-OCOCH ₃ -CH ₂ -ζ " 0 -CH ₂ CN CH 6-CH ₃ H -Chg-OCOCH J 0 -C ₂ Hg ^CH 3 6-CH ₃ H -Chg-OCOCH I 0 -CH ₉ CHgOCH ₃ CH ₃ 6-CH ₃ . H -CH ₂ -OCOCH ₃ I 0 -Chg-CH = CHg ^CH 3 6-CH ₃ H . -CHg-OCOCH ₃ - ^CH * -Vl 0 -CH ₂ -CSCH CH ₃ 6-CH ₃ H -Chg-OCOCH -CH ₉ -N 0 -CHgCHgOCgHg ^CH 3 6-CH ₃ H. -Chg-OCOCH 0 -C ₂ H ₄ OC ₂ H ₄ OCH ₃ CH ₃ 6-CH ₃ H -Chg-OCOCH ^ 0 -CH ₂ CN H H H -CH ₉ -N * Vj- 0 -CH ₃ H H H 0 -C ₂ Hg H H H 0 -C ₂ H ₄ OCH ₃ H H H 0 -CH ₂ -CH = CH ₉ H H H 0 -Chg-C = CH H H H 0 -CgH ₄ OCgH ₅ H H H 0 -C ₂ H ₄ OC ₂ H ₄ OCH

10.12.1980 56 991/11

R ¹ R ² R ³

, 4

H .

CH_ 6-CH

CH_ 6-CH H

CH. 6-CH_ H

CH 6 -CH ₃ H

CH ₃ 6 -CH ₃ H

CH ₃ 6 -CH ₃ "H-

CH ₃ 6 -CH ₃ H

-N

/ = R N

-CH ₂ -Nl

-CH ₂ -f

-CH _n -N

U

/ = N

N =

-CH ₂ -

-ChL

- ^C 2 ^H 5 5 - ^C 2 H ₄ OCH ₄ 0CH ₃ -CH -CH -C _{2 2} -CH = CH ₂ - ^C 2 ₂ -CCH -CH H ₄ OC ₂ H H ₄ OC ₂ H ₂ CN

CH, 6-C _o H_H

ό ei O

CH_ 6 "" C _O H_ H

CH.

CH_

CH ₃ 6-C ₂ H ₅ H CH- 6-C ₀ H- H

CH-6-C _o H _c H ύ do

-CH ₂ -N, N- 0 l -C ₂ H ₄ OCH ₃ -CH ₂ -N O -CH ₂ -CH = CH -CH ₂ ¹ 0 -CH ₂ -C ₅ CH -CH ₂ -C -C ₂ HOC ₂ H

CH

-CH ₀ -N

² years ago

-C ₂ H ₄ OC ₂ H ₄ OCH ₃

20358

10.12.1980 56 991/11

CH 6-C ₉ HH

H H

H H

^CH 3 H ^CH 3 H Cl 6-CH Cl 6-CH Cl 6-CH Cl 6-CH Cl 6-CH C (CH ₃ ) ₃ H C (CH ₃ H ^H C (CH ₃ H ^H C (CH ) H

-CH ₀ -

-CH ₉ -N j

* Yj = ¹

--CHCl ^

CH ₂ OCH

-CH

-CH ₉ -N.

0 0

-lsiΓΊ ο Vi = J

H -CHCl ₂ 0 H 0 H -CH ₂ OCH ₃ 0 H -CH ₂ -J = 0

CH ₂ CN

0 -CH.

-CH

-CH

0 -CH

3

-CH

Vl = I

0 -CH,

-CH

-CH

-CH

-CH

0 -CH.

C (CH ₃ J ₃ H

CH ₃ 4 -CH ₃ 6-CH ₃

-CHCl 0 0

-CH

CH, 4-CH, 6-CH, -CH ₀ OCH

οό ό c. ό

0 -CH.

10.12.1980 56 991/11

R-

CH_ 4-CH "6-CH

CH.

CH ₃ 4-CH _3, 6-CH ₃ -N -Chg

CH.

CH ₃ 4-CH ₃ 6-CH ₃ H H -CHCIg ι- ι] 0 -CH ₃ H H H - S -CH ₃ H H H J S - ^C 2 ^H 5 H H H S -Chg-CH = CHg H H H S 1 -Chg-CSCH ^CH 3 6-CH ₃ H S -CH ₃ ^CH 3 6-CH ₃ H - ¹ V ¹ S - ^C 2 ^H 5 ^CH 3 6-CH ₃ H S -Chg-CH = CHg ^CH 3 6- CH H  Φ S -Chg-CSCH ^CH 3 ⁶ ~ ^C 2 ^H 5 H S -CH ₃ ^CH 3 6-CgH ₅ H S - ^C 2 ^H 5. CH ₃ 6-C ₂ H ₅ S -Chg-CH = CHg ^CH 3 6-C ₂ H ₅ S -Chg-CSCH

2203 ³⁰ - 26 - R ⁴ 10 Y .12.1980 R ² R ³ 56 S 991/11 R ¹ 6-CH ₃ H S R Cl 6-CH ₃ H S -CH ₃ Cl 6-CH ₃ H S - ^C 2 ^H 5 Cl 6-CH ₃ H " S -CHp-CH = CHp Cl H H S -Chg-C = CHg ^CH 3 H H S -CH ₃ ^CH 3 H H S -CgH ₅ CH ₃ H H S -Chg-CH = CHg CH ₃ 3) 3 ^H H Q S -Chg-CSCH C (CH 3- ^ 3 ^H H S -CH ₃ C (CH 3) 3 ^H H S ~ ^C 2 ^H 5 C (CH 3) 3 ^H H 0 S -Chg-CH = CHg C (CH 4-CH ₃ 6-CH ₃ O S -Chg-C = CH CH ₃ 4-CH ₃ 6-CH ₃ O S -CH ₃ CH ₃ 4-CH ₃ 6-CH ₃ O S - ^C 2 ^H 5 CH ₃ 5-CH -Chg-CH = CHg CH ₃ -CHp-C = CH

10.12.1980 2 2 0 3 5 8 - 27 - 56 991/11

R ¹ R ² R ³ R ⁴ Y R H H H -CH ₂ OCH ₃ S -CH ₃ H H H -CHgOCH ₅ S - ^C 2 ^H 5 H H H -CHgOCH ₃ S - CHp-CH = »CH <-j H H H -CHgOCH ₃ S -CHp-C = CH ^CH 3 6-CH ₃ H -CHgOCH ₃ S -CHJ ^CH 3 6-CH ₃ H -CHgOCH ₃ S CH ₃ 6-CH ₃ ^ H -CH ₀ OCH, S -Chg-CH = CHg ^CH 3 6-CH ₃ H -CHgOCH ₃ S " CHq-C = CH CH ₃ 6-CgH ₅ H -CHgOCH ₃ S -CH ₃ ^CH 3 6-CgH ₅ H -CHgOCH ₃ S -C ₂ H ₅ CH ₃ 6-C ₂ H ₅ H -CHgOCH S -Chg-CH = CHg CH ₃ 6-CgH ₅ H -CHgOCH S -Chg-CSCH Cl 6-CH ₃ H -CHgOCH ₃ S -CH ₃ Cl 6-CH ₃ H -CHgOCH S -C ₂ H ₅ Cl 6-CH ₃ H -CH ₂ OCH ₃ S -Chg-CH = CHg Cl 6-CH ₃ H -CHgOCH ₃ S -Chg-C = CH ^CH 3 H H -CHgOCH ₃ S -CH ₃ CH ₃ H H -CHgOCH ₃ S - ^C 2 ^H 5 ^CH 3 H H -CHgOCH ₃ S -Chg-CH = CHg

220358 -28-

10.12.1980 56 991/11

^CH 3 H H -CHgOCH S -Chg-CSCH C (CH ₃ J ₃ H H -CH ₀ OCH- S -CH ₃ C (CH ₃ ) ₃ H H -CHgOCH ₃ S ~ ^C 2 ^H 5 C (CH) H H -CH ₀ OCH- 2 3 S -Chg-CH = CHg C (CH ₃ ) ₃ H H -CH ₀ OCH, 2 3 S -CH ₀ -C = CH ^CH 3 4-CH ₃ 6-CH3 -CH OCH S -CH ₃ CH ₃ 4-CH ₃ 6-CH, -CH ₂ OCH S - ^C 2 ^H 5 CH ₃ 4-CH ₃ 6-CH3 -CHgOCH ₃ S -CH ₂ -CH = CH _? ^CH 3 4-CH ₃ 6-CH ₃ -CHgOCH ₃ S -CHq-C = CH H H H -CHg -N ~~ S -CH ₃ H H H -CHg -N ~ S - ° 2 ^H 5 H H H -CH ₂ ^ Q S -Chg-CH = CHg H H H -CHg -N "~ S -Chg-CSCH CH ₃ 6-CH ₃ H -CHg -N "~ S -CH ₃ ^CH 3 6-CH ₃ H --2 -V S - ^C 2 ^H 5 ^CH 3 6-CH ₃ H -CH ₂ -N ^ S -Chg-CH = CHg

22C ) 358 H - 29 - R ⁴ Y 12/10/1980 R ² R ³ " H S 56 991/11 R ¹ 6-CH ₃ H -Chg -Q S R CH, Δ 6-CH ₃ H -Chg Vj =. S -Chg-C ^ CH Cl 6-CH ₃ H -CH ₂ S -CH ₃ Cl 6-CH ₃ H -Chg -C ~ ^C 2 ^H 5 Cl 6-CH ₃ H -Chg -C S -Chg-CH = CHg Cl H H -Chg -C ⁵ -Chg-CSCH ^CH 3 H H -Chg -Cl S -CH ₃ ^CH 3 H H -Chg S -CgH ₅ ^CH 3 H H -CH _? -G S - Utip- ΟΠ = ΟΠρ Chg 3) 3 ^H H -Chg -N ~ N = I - -Chg-CHCH C (CH 3) 3 ^H H -Chg -N. "" S -CH ₃ C (CH 3) 3 ^H -Chg S -CgH ₅ C (CH 3 ^} 3 ^H -Chg -Chg-CH = CHg C (CH -Chg-C = CH

2203 158 - * 30 - R ⁴ Y 12/10/1980 R ² R ³ - α S 56 991/11 R ¹ 4-CH 6-CH ₃ -Chg -Q S R ^CH 3 4-CH ₃ 6-CH ₃ -Chg -CH ₃ CH ₃ - ^C 2 ^H 5

CH ₃ 4 -CH ₃ 6 -CH- -CHg -NS-CHG-CH = CHg CH ₃ 4 -CH ₃ 6 -CH ₃ -CHg -NI S -CHg-C = CH

10.12.1980 56 991/11

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

CH

CH.

CH

Il

C - OCH.

Cl-CO-CH ₂ OCH

CH C-OCH.

C-CH ₂ OCH ₃

If, for example, N-dichloroacetyl-N ~ (2,6-xylyl) ethylglycine and propargyl alcohol are used as starting materials and DCC as condensing agent, the course of the reaction can be represented by the following formula scheme (process b):

CH

CH.

^C 2 ^H

CH

0 Il C-OH

- CHCl

+ HO-CH ₂ -C =CH

+ DCC "

~ DCH

CH 0

r ⁵ H

CH is C-O-CH-C = CH

* DCC = dicyclohexylcarbodiimide 'dch = dicyclohexylurea f

10.12.1980 56 991/11

If, for example, N- (2-furoyl) -N ~ (2,6-xylyl) -ethyl-glycine chloride and O-methylglycol are used as starting materials, the course of the reaction can be represented by the following formula scheme.

CH

HO-Chuchu-OCH

3 ^ .CH CO-CH ₂ CH ₂ OCH ₃

If, for example, N-chloroacetyl-N- (2,6-xylene) "ethylglycine methyl ester and imidazole are used as starting materials, the course of the reaction can be represented by the following formula scheme (method d):

CH.

f2 ^H5 CH- 0 Il - C-OCH-Cl 3 · » C "H, 2 5, CH -C-CH ₀ - O + Base C-CH ₀ Ii ² Q HCl 0 0 Il C-OCH -N Ί , ^CH 3 CH ₃

If, for example, N-hydroxyacetyl-N ~ (2,6-xylyl) ethylglycine methyl ester and ethoxymethyl chloride are used as starting materials, the course of the reaction can be represented by the following formula scheme (process e / 1):

22035

10 * 12.1980 56 991/11

CH.

CH ₅

CH C »0CH.

C-CH ₀ -OH "

+ Cl-CH ₂ -OC ₂ H ₅

+ Base -HCl

CH.

CH 0 I ^ ^D If CH C-OCH.

OCH ₀ -O-CH ₀ -OC ₀ H- "2 2 2 5

If, for example, N-hydroxyacetyl-N ~ (2,6-xylyl) ethyl-glycine methyl ester and 3,4-dihydro-4H-pyran are used as starting materials, the course of the reaction can be represented by the following formula scheme (process e / 2):

CH.

CH

CH

r ^b ti

CH C-OCH.

C-CH ₀ OH

catalyst

CH.

CH C-OCH

10.12.1980 220358-34- 56 991/11

For carrying out the process (a) required as starting materials N-phenyl-ethylglycin- (thiol) esters are generally defined by the formula (II)

In this formula, R, R, R, R and Y are preferably those radicals which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention.

The N-phenyl-ethylglycine (thiol) esters of the formula (II) are described in part (cf. US Pat. No. 4,096,167 and DE-OS No. 28 05 525). They can be obtained by reacting ζ, B * with corresponding anilines "<-Halogenbuttersäure (thiol) esters in the presence of an acid binder, such as potassium carbonate and in the presence of an inert organic solvent such as dimethylformamide, and optionally in the presence of a catalyst, such as, _e B _e potassium iodide, at temperatures between 20 and 100 ⁰ C implements.

The N-phenyl-ethylglycine (thiol) esters of the formula (II) can also be obtained if N-phenylethylglycines are reacted with corresponding alcohols or thiols by known processes, eg. B "in the presence of boron trifluoride, esterified (see also the information for the method b) _e

As examples of the starting materials of the formula (II)

be named:

CH 0

- I ^{2 5} I!

_R 2 .R ^x CH- C - Y - R

10.12.1980 - 35 - 56 991/11

R ¹ . R ² H R ³ Y R H H H 0 (S) -CH ₃ H H H O (S) " ^C 2 ^H 5 H H H O (S) CH ^ CHRT-0 CH_ H H H O (S) -Chg-CH = CH ₂ H H H "0" (S) - CHjj-C ^ CH H H H O (S) -CHgCHg-O-CgHg H 6-CH ₃ H P (S) -C ₂ H ₄ -OC ₂ H ₄ -OCH ₃ ^CH 3 , 6-CH, H O (S) -CH_ 3 ^CH 3 6-CH ₃ H O (S) - ^C 2 ^H 5 CH ₃ 6-CH ₃ H O (S) -CHgCHg-O-CH CH ₃ 6-CH ₃ H O (S) «> CHp -CH = CH ^ ^CH 3 6-CH ₃ H O (S) -CH ₂ -CSCH ^CH 3 6-CH ₃ H O (S) -CHgCHg-O-CgHg ^CH 3 6 -C ₂ H ₅ H O (S) " ^C 2 ^H 4" ° " ^C 2 ^H 4 ~ ^CH 3 ^C 2 ^H 5 6-C ₂ Hg H O (S) -CH ₃ ^C 2 ^H 5 6-CgHg H O (S) • - ^C 2 ^H 5 CgH ₅ 6-CgHg H O (S) -CHgCHg-O-CH ₃ CgHg 6-CgH ₅ H O (S) -Chg-CH = CH ₂ ^C 2 ^H 5 6 ^ C ₂ Hg H O (S) -CH ₂ -CSCH ^C 2 ^H 5 6-C ₂ H ₅ H O (S) -CHgCHg-O-CgHg ^C 2 ^H 5 6-CH ₃ H O (S) "* ^C 2 ^H 4" ° " ^C 2 ^H 4" ^0CH 3 ^C 2 ^H 5 6-CH H O (S) , , - ^CH 3 ^C 2 ^H 5 H O (S) -C ₂ H ₅

10.12.1980 - 36 - 56 991/11

R ¹ H R ² R ³ Y R ^C 2 ^H 5 ₃ 6-CH ₃ H O (S) -CH ₀ CH ₀ -O-CH- ^C 2 ^H 5 ₃ 6-CH ₃ H' O (S) -Chg-CH = CHg ^C 2 ^H 5 > 3 6-CH ₃ H O (S) -Chg-CSCH ^C 2 ^H 5 > 3 6-CH ₃ H O (S) -CHgCH ₂ -O-CgH ₅ ^C 2 ^H 5 6-CH ₃ H O (S) -CgH ₄ -O-CgH ₄ -OCH ₃ v / 1 «v ·» A ₇ H H H 0 (SJ -CH ₃ C (CH ₃ H H • O (S) -CgH ₅ C (CH ₃ H H O (S) -CHgCH ₂ -O-CH ₃ C (CH ₃ H • H O (S) -Chg-CH = CHg C (CH ₃ H H O (S) -CH ₀ -C = CH C (CH ₃ H H O (S) -CHgCH ₂ -O-CgH ₅ C (CH ₃ H H 0 (SJ -CgH ₄ -O-CgH ₄ -OCH ₃ CH ₃ 3-CH ₃ H 0 (SJ -CH ό ^CH 3 - _ . 3-CH ₃ H O (S) - ° 2 ^H 5 ^CH 3 3-CH ₃ H O (S) -CHgCHg-O-CH ^CH 3 3-CH ₃ H 0. (S) -Chg-CH = CHg ^CH 3 3-CH ₃ H O (S) -Chg-CSCH CH ₃ 3-CH ₃ H O (S) -CHgCH ₂ -O-CgH ₅ ^CH 3 3-CH ₃ H O (S) -C ₂ H ₄ -O-CgH ₄ -OCH ₃ ^C 2 ^H 5 H H O (S) -CH ₃ ^C 2 ^H 5 H H O (S) " ^C 2 ^H 5 ^C 2 ^H 5 H H O (S) -CHgCH ₂ -O-CH ₃ ^C 2 ^H 5 H H 0 (S) -Chg-CH = CHg ^C 2 ^H 5 H H O (S) -Chg-CSCH CgH ₅ H H O (S) -CHgCHg-OC ₂ H ₅ ^C 2 ^H 5 H H 0 (SJ -CgH ₄ -O-CgH-OCH

220358

- * 37 -

10.12.1980 56 991/11

XC ₃ H ₇ H H O (S) -CH ₃ XC ₃ H ₇ H H O (S) - ^C 2 ^H 5. AC ₃ H ₇ H H O (S) -CHgCHg-O-CH XC ₃ H ₇ H H O (S) -Chg-CH = CHg XC ₃ H ₇ "' H H O (S) -Chg-CSCH XC ₃ H ₇ H , H O (S) ^ CHgCH ₂ -O-CgH ₅ XC ₃ H ₇ H H O (S) -C ₂ H ₄ -O-CgH ₄ -OCH ₃ CH ₃ 5-CH ₃ H O (S) -CH ₃ ^CH 3 5-CH ₃ H O (S) -C ₂ H ₅ ^CH 3 5-CH ₃ H O (S) -CHgCHg-O-CH ₇ CH ₃ 5-CH ₃ H O (S) -Chg-CH = CHg ^CH 3 5-CH3 H O (S) -Chg-CSCH CH ₃ 5-CH ₃ H O (S) -CHgCH ₂ -O-CgH ₅ ^CH 3 5-CH ₃ H 0 (S) -CgH ₄ -O-CgH ₄ -OCH ₃ Cl 6-CH ₃ H O (S) -CH ₃ Cl 6-CH ₃ H O (S) " ^C 2 ^H 5 Cl 6-CH ₃ H O (S) -CH ₀ OH ₉ -O-CH, 2 * - "3 Cl 6-CH ₃ H 0 (3) -Chg-CH = CHg Cl 6-CH ό H O (S) -Chg-C £ CH Cl 6-CH ₃ H O (S) -CHgCHg-O-CgH ₅ Cl 6-CH ₃ H O (S) -CgH ₄ -O-CgH ₄ -OCH

10.12.1980 - 38 - - 56 991/11

R ¹ R ² H R ³ Y R Cl 6-C (CH ₃ H O (S) -CH ό Cl 6-C (CH _{3 3} H O (S) - ^C 2 ^H 5 Cl 6-C (CH H H O (S) -CHgCHg-O-CH Cl 6-C (CH ₃ H O (S) -Chg-CH = CHg Cl 6-C (CH H ' H O (S) -Chg-C £ CH Cl 6-C (CH ₃ '3 H O (S) -CHgCH ₂ -O-CgH ₅ Cl 6-C (CH ₃ H O (S) -CgH ₄ -O-CgH ₄ -OCH ₃ ^CH 3 3-CH ₃ 6-CH ₃ O (S) -CH ₃ ^CH 3 3-CH ₃ 6-CH ₃ O (S) - ^C 2 ^H 5 ^CH 3 3-CH ₃ 6-CH ₃ O (S) -CHgCHg-O-CH ₃ ^CH 3 3-CH ₃ 6-CH ₃ O (S) -Chg-CH = CHg CH ₃ 3-CH ₃ 6-CH ₃ O (S) -Chg-C = CH ^CH 3 ³ " ^CH 3 6-CH ₃ O (S) -CH ₂ CH ₂ -O-CgH ₅ ^CH 3 3-CH ₃ 6-CH ₃ O (S). -CgH ₄ -O-CgH ₄ -OCH ₃ CH ₃ 4-CH ₃ 6-CH, O (S) -CH CH ₃ 4-CH ₃ 6-CH ₃ O (S) -CgH ₅ ^CH 3 4-CH ₃ 6-CH ₃ O (S) -CH ₂ CH ₂ -O-CH ₃ ^CH 3 4-CH ₃ 6-CH ₃ O (S) -Chg-CH = CH ₂ CH ₃ 4-CH ₃ 3 O (S) -Chg-C = CH ^CH 3 4-CH ₃ 6-CH_ O (S) -CHgCH ₂ -O-CgH ₅ ^CH 3 4-CH 6 «CH ₃ O (S) -CgH ₄ -O-CgH ₄ -OCH

19mi!) 80 * l

10.12.1980 - 39 - 56 991/11

R ¹ R ² R ³ Y- R 1-C ₃ H ₇ 6-SrX-C ₃ H ₇ H 0 (S) -CH ₃ 1-C ₃ H ₇ 6-XC ₃ H ₇ H O (S) ~ ^C 2 ^H 5 XC ₃ H ₇ 6-iC H ό / H O (S) -CHgCH ₂ -O-CH ₃ 1-C ₃ H ₇ 6-iC, H ₇ H O (S) -Chg-CH = CHg 1-C ₃ H ₇ 6-XC ₃ H ₇ H O (S) -Chg-C = CH XC ₃ H ₇ 6-1-C ₃ H ₇ H O (S) -CHgCH ₂ -O-CgH ₅ 1-C ₃ H ₇ 6-XC ₃ H ₇ H • o (s) -CgH ₄ -OC ₂ H ₄ -OCH ₃ OCH ₃ 6-CH3 H O (S) CH, 0CH_ 3 6-CH ₃ H O (S) - ^C 2 ^H 5 OCH, 6-CH ₃ H O (S) -CHgCHg ^ O-CH ₃ OCH ₃ 6-CH ₃ H O (S) -Chg-CH = CHg ' ^0CH -2 6-CH ₃ H O (S) -Chg-C = CH OCH ₃ 6-CH ₃ H O (S) -CH ₂ CH ₂ -O-CgH ₅ OCH ₃ 6-CH3. H O (S). -CgH ₄ -O-CgH ₄ -OCH ₃ br 6-CH ₃ H O (S) -CH ₃ br 6-CH ₃ H O (S) - ^C 2 ^H 5 br 6-CH ₃ H O (S) -CHgCHg-O-CH br 6-CH ₃ H O (S) -Chg-CH = CHg br 6-CH3 H O (S) -Chg-C = CH br 6-CH ₃ H O (S) -CHgCH ₂ -O-CgH ₅ br 6-CH, H O (S) -CgH ₄ -O-CgH ₄ -OCH

10,12.1980

2 2 0 3 5 8 - 40 - 56 991/11

R ¹ R ² R ³ Y R OCH ₃ 6-OCH, H 0 (S) -CH ₃ OCH • 6 ochs H O (S) - ° 2 ^H 5 OCH ₃ 6-OCH ₃ H O (S) -CHgCHg-O-CH OCH 6-OCH H O (S) -Chg-CH = CHg OCH ₃ 6-OCH ₃ H 0 (S) -Chg-C = CH OCH ₃ 6-0CH " 0 H O (S) -CHgCH ₂ -O-CgH ₅ OCH 6-OCH ₃ H O (S) -CgH ₄ -O-CgH ₄ -OCH ₃

The acid chlorides and bromides or anhydrides which are also to be used as starting materials for process (a) according to the invention are generally defined by the formulas (IIIa) and (IIIb). In these formulas, K stands! preferably for those radicals which have already been mentioned as preferred in connection with the description of the substances of the formula (I) according to the invention for this substituent.

• 10.12.1980 2 2 0 3 5 8 - 41 - 56 991/11

The acid chlorides and bromides or anhydrides of the formulas (IIIa) and (IIIb) are generally known compounds of organic chemistry *

To be used in the for process variant (b) as starting materials N-acyl-N-phenyl-ethylglycine are represented by the formula (IV) is generally defined In this formula, u * £ * £ ^an d R preferably represents the residues with related the description of the substances of the formula (I) according to the invention have already been mentioned preferably for these substituents.

The N-acyl-N-phenyl-ethylglycines of the formula (IV) are not yet known. However, they can be obtained in a simple manner by aer N-phenyl-ethylglycine with acid chlorides formula (IIIa) in the presence of an acid binder such as sodium hydroxide and in the presence of an inert organic solvent such as methylene chloride at temperatures between 0 and 120 ⁰ C implements.

In addition, the alcohols or thiols to be used as starting materials for process variants (b) and (c) are generally defined by the formula (V). In this formula, JR and Y are preferably the radicals which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention »

The alcohols or thiols of the formula (V) are generally known compounds of organic chemistry,

10,12,1980 220358 «42- 56 991/11

The N-acyl-N-phenyl-ethylglycine chlorides to be used as starting materials for process variant (c) are generally defined by the formula (VI). "In this formula, R, R, F? and R ₁ preferably for the radicals which have already been mentioned in connection with the description of the substances of the formula (I) according to the invention preferably for these substituents.

The N-acyl-N-phenyl-ethylglycine chlorides of the formula (VI) are not yet known. However, they can be obtained in a simple manner by reacting the N-acyl-N-phenylethylglycines of the formula (IV) preferably with oxalyl chloride in the presence of Implemented dimethylformamide or pyridine.

For carrying out the process (d) required as starting materials N ~ chloroacetyl-N ~ phenyl »ethylglycine (thiol) esters are generally defined by the formula (VII). In this formula, R.sup.1, R.sup.1, R.sup.2 and R.sup.4 preferably represent those radicals which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention *

The N-chloroacetyl-N-phenyl-ethylglycinfthiol) esters of formula (VII) are partially described (see US-PS 4,095,167 and DE-OS 28 05 525). They can be obtained by z. B ₆ N-phenyl-ethylglycine (thiol) ester of the formula (II) according to the process variant (a) with chloroacetic acid chlorides.

10.12.1980 220358 -43- 56 991/11

The compounds which are furthermore to be used as starting materials for process (d) according to the invention are generally defined by the formula (VIII). In this formula, Az_ and R ~ preferably represent those radicals which have already been mentioned as preferred in connection with the description of the compounds of the formula (I) according to the invention for these substituents. Preferably, JB is hydrogen, sodium and potassium.

The compounds of formula (VIII) are well-known compounds of organic chemistry.

The N-hydroxyacetyl-N-phenylethylglycine (thiol) esters required as starting materials for carrying out the process (e) according to the invention are generally represented by the formula (IX)

12 3 mine defines. In this formula, _R _f _R, _R and IR are preferably those radicals which have already been mentioned as preferred for these substituents in connection with the description of the substances of the formula (I) according to the invention.

The N-hydroxyacetyl-N-phenyl-ethylglycine (thiol) esters of the formula (IX) are compounds according to the invention. They can also be obtained by

f) N ~ Acyloxyacetyl ~ N-phenyl-ethylglycine (thiol) ester of the formula

C___ / ~> V D - O - t - ix

N 7

C - CH ₉ - O - CO - R ⁸

-O 10,12,1980

2 2 0 3 0 O *. 44 - 56 991/11

in which

and R have the abovementioned meaning and

R ^{8 is} alkyl having 1 to 4 carbon atoms,

with sodium or potassium hydroxide in aqueous or alcoholic solution, ζ, Β _β saponified in methanol or ethanol, at temperatures between 20 and 60 C and after acidification with compounds of formula (V) in the presence of an esterification catalyst, such as B _e , boron trifluoride , esterified.

The acyloxyacetylanilides of the formula (XII) are likewise compounds according to the invention and can be obtained by the process variants (a) and (d) described above.

The also for the process according to the invention (e / 1) as starting materials to be used halides are generally defined by the formula (X). In this formula are F? and shark preferably for the radicals specified in the definition of the invention,

The halides of formula (X) are known compounds sind.allgemein aer organic chemistry,

The process of the invention (e / 2) also as a raw material to be used dihydropyran is also a known compound aer organic chemistry,

•, 10.12.1980

22Q35 8 - 45 - '56 991/11

Suitable diluents for the reaction according to the invention in process (a) are preferably inert organic solvents. These include, preferably, ketones, such as diethyl ketone, in particular acetone and methyl ethyl ketone; Nitriles, such as propionitrile, in particular acetonitrile; Ethers, such as tetrahydrofuran or dioxane; aliphatic and aromatic hydrocarbons, such as petroleum ether, benzene, toluene or xylene, · halogenated © hydrocarbons, such as methylene chloride, carbon tetrachloride, chloroform or chlorobenzene and esters, such as ethyl acetate.

If appropriate, the process (a) according to the invention can be carried out in the presence of acid binders CCrom (bromine) hydrogen acceptors 3; as such, all common acid binders can be used. These include organic bases, preferably tertiary amines, such as. B, triethylamine and pyridine; Further, inorganic bases such as _{# # #} alkali hydroxides and alkali carbonates. As a catalyst in particular dimethylformamide is considered.

The reaction temperatures can be varied within a substantial range in carrying out process (a) according to the invention. In general, one works between O and 120 ⁰ C, preferably between 20 and 100 ⁰ C.

In carrying out the process (a) according to the invention, it is preferable to use 1 mol of the compounds of the formula (II) if R is not hydroxyalkyl, 1 to 1.5 mol of the compounds of the formula (III) and optionally 1 to 1, 5 mol of acid binder.

10.12,1980

2 2 0 3 5 8 - ⁴⁶ - ^{56 991} Z ¹¹

However, if R is hydroxyalkyl in these starting compounds, 2 to 2 _{f of} 5 mol of the compounds of the formula (III) and, if appropriate, 2 to 2.5 mol of acid binder are employed per 1 mol of this compound. The isolation of the compounds of the formula (I) takes place in the usual way.

As the solvent, preferably inert organic solvent in Frag © _e for this purpose are for the reaction in process variant (b) include, preferably, aromatic hydrocarbon such as benzene »toluene or xylene; halogenated hydrocarbons, such as chloroform or dichloromethane, esters, such as ethyl acetate; Ethers, such as tetrahydrofuran, and the alcohols (thiols) used as the reaction component itself.

The process according to the invention (b) is carried out in the presence of a condensing agent; as such, all conventional condensing agents can be used, such as in particular dicyclohexylcarbodiimide (DCC), ethyl chloroformate or benzenesulfonyl chloride.

The reaction temperatures could be varied within a relatively wide range when carrying out the process (b) according to the invention. "In general, the reaction is carried out at between 0 and 150 ^° C., preferably between 20 and 100 ^° C., or at the boiling point of the solvent used.

In ä r & carrying out the method according to the invention (b) are preferably employed to 1 mol of the compounds of formula (IV) from 2 to 8 moles of alcohol (thiol) and 1 to 2 mol of condensing agent. The isolation of the compounds of formula (I) is carried out in the usual way *

10.12.1930 • 22Q358 1 47 -. 56 991/11

Suitable solvents for the inventive reaction according to process variant (c) are preferably inert organic solvents. These include preferably in process variant (-θ) already preferably mentioned solvates. The process may optionally be carried out in the presence of an organic or inorganic base; Preferred bases were named in discussion of procedure (a).

The reaction temperatures can be varied within a substantial range when carrying out process variant (c). In general, the reaction is carried out between 0 and 120 ^° C., preferably between 20 and 100 ^° C., or at the boiling point of the particular solvent.

When carrying out process variant (c), the reaction is preferably carried out in molar amounts. The isolation of the compounds of formula (I) is carried out in the usual way *

Preferred diluents for the reaction according to the invention in process (d) are inert organic solvents. These preferably include the solvents already mentioned in process (a).

The reaction according to process (d) can optionally be carried out in the presence of an acid binder. It is possible to add all customary inorganic or organic acid binders, such as alkali metal carbonates, for example sodium carbonate, potassium carbonate and sodium bicarbonate; or lower tertiary alkylamines, cycloalkylamines or aralkylamines, for example triethylamine, dimethylbenzylamine; or pyridine and diazabicyclooctane. Preferably, an excess of azole is used.

-. 10.12.1980 - 48 - '56 991/11

The reaction temperatures can be varied within a broad range in process (d). In general, one works between about 20 to 150 C, preferably at 60 to 120 ⁰ C. In the presence of a solvent is advantageously carried out at the boiling point of the respective solvent,

Bai the implementation * of the process (d) is used for 1 mol of the compounds of formula (VII) is preferably 1 to 2 moles of the compounds of formula (VIII) and optionally 1 to 2 moles of acid binder. The isolation of the compounds of the formula (I) is carried out in the usual way. ·

Preferred diluents for the reaction according to the invention in process (e) are inert organic solvents. These preferably include the solvent already mentioned in process (a).

The reaction according to process (e / 1) can optionally be carried out in the presence of an acid binder. It is possible to add commonly used inorganic or organic acid binders. These preferably include the compounds already mentioned in process (a).

The reaction temperatures can be varied within a wide range in process (e / 1). In general, one works between 20 and 150 C, preferably at the boiling point of the solvent, for example between 60 and 100 ° C «

In carrying out the process (e / 1) according to the invention, use is made of 1 mol of the compounds of the formula (IX),

10 * 12.1980 220358 - 49 - 56 991/11

optionally after the addition of 1 to 2 moles of a strong base such as ζ "B, an alkali metal hydride, 1 mol of halide aer formula (X) and optionally 1 to 2 moles of acid-binding agent. To isolate the end products, the reaction mixture is freed from the solvent and the residue is mixed with water and an organic solvent »The organic phase is separated and worked up in the usual manner»

According to a preferred embodiment of the process (e / 1), it is expedient to proceed by starting from a hydroxyacetanilide of the formula (IX), converting the latter into the alkali metal alkoxide by means of an alkali metal hydride or bromide in a suitable inert solvent »and the latter without isolation immediately reacted with a halide aer formula (X), wherein the exit of alkali halide, the compounds of formula (I) according to the invention are obtained in one operation.

The reaction according to process (e / 2) can optionally be carried out in the presence of a catalyst. For this purpose, hydrogen chloride is preferably used (compare D, Am Chem * Soc 69, 2246 (1947), ibid., 70, 4187 (1948)).

The reaction temperatures can be varied within a wide range in process (e / 2). In general, one works between 0 and 100 ⁰ C, preferably between 20 and 60 ⁰ C.

When carrying out the process (e / 2) according to the invention, the reaction is preferably carried out in molar amounts. The isolation of the compounds of the formula (I) is carried out in the customary manner.

10 »12.1980 - 50 - 56 991/11

The active compounds according to the invention have a strong microbicidal action and can be used practically for controlling unwanted microorganisms. The active compounds are suitable for use as crop protection agents.

Crop protection fungicides are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes * Deuteromycetes.

The good plant tolerance of the active ingredients in the concentrations necessary for the control of plant diseases allows a treatment of aboveground plant parts, of plant and seed and the soil »

As plant protection agents, the active compounds according to the invention can be? substances with particular success in the fight against oomycetes, ζ. Β _β against the herbaceous and brown rot pathogen of tomato and potato (Phytophthora infestans). It should be emphasized that the active compounds according to the invention not only have a protective, but also a curative / eradicative effect. In addition, they have systemic properties "So it is possible to protect plants against fungal attack when the active ingredient on the soil and the root or the seed feeds the aerial parts of the plant.

10.12.1980 2 2 0 3 5 8 - '- * 51 -. 56 991/11

The active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active ingredient-impregnated natural and synthetic substances, microencapsulations in polymeric substances and in seed coating compositions, and also in formulations with fuel assemblies, such as smoking cartridges, cans, spirals, etc., as well as ULV-KaIt and warm mist formulations »

These formulations are prepared in a known manner, z, B, by mixing the active compounds with extenders, ie liquid solvents, liquefied gases under pressure and / or solid carriers, optionally with the use of surface-active agents, emulsifiers and / or dispersants and / or foaming agents. In the case of using water as an extender z. As well as organic solvents can be used as auxiliary solvent. Suitable liquid solvents are essentially: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for. B, petroleum fractions, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water; by liquefied gaseous diluents or carriers are meant those liquids which are gaseous at normal temperature and under normal pressure, eg, aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid

10.12.1980 220358 ~ 52 ~ 56 991/11

Carriers come into question: z. B, ground natural minerals * such as kaolins, clays * talc, chalk / quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as fumed silica, alumina and silicates; As solid carriers for granules are: z. B _e crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust ,, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam formers are: B, nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, Z, B, alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates and protein hydrolytes sate; as dispersants in question: z. B _# lignin-sulphite liquors and methylcellulose,

Adhesives, such as carboxymethylcellulose, natural and synthetic powdery, granular or latex-type polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, can be used in the formulations.

It may dyes, such as inorganic pigments ,, z. B, iron oxide, titanium oxide, ferrocyan blue, and organic dyes such as alizarin, azole metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum, and zinc.

The formulations generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90 %.

  12/10/1980

220358 -53- 56 991/11

The active compounds of the invention may be present in the formulations or in the various forms of application in admixture with other known active substances, such as fungicides, bactericides, insecticides, acaricides, nematicides, herbicides, bird repellants, growth factors, plant nutrients and soil conditioners *

The active substances can be used as such in the form of their formulations or daärauo. used by further dilution, such as ready-to-use solutions, emulsions, suspensions, powders, pastes and granules. The application is carried out in a customary manner, for example by pouring, dipping, spraying, spraying, atomizing * vaporizing, injecting, silting, spreading, dusting, spreading, dry pickling, moist pickling, wet pickling, slurry pickling or encrusting.

In the treatment of parts of plants, the drug concentrations in the use forms can be varied within a substantial range. They are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001 % _t

In the seed treatment, in general, amounts of active ingredient of 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g, needed.

When treating the soil, drug concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02 %, are required at the site of action.

10,12.1980 - 54 -. 56 991/11

In the following examples the following compounds are used as reference substances:

0 CH, - Il

⁰ CH ₀ - C - 0 - CH_ < ²

^ C-CH ₀ Cl

pu ti £

^GH 3 0

N-chloroacetyl ~ N- (2,6 "> xylyl) glycine methyl ester

CH, 0

/ ri CH-CO-CH

(B) = <O> ~ N ^ ²

^xv ^ <^ C- CH ₀ Cl

CH " ^d C ₂ H _{5 O}

N-ChIoracetyl-N- (2-ethyl-6 ~ methylphenyl) alanine methyl ester

10,12.1980

22 0 35 8 ~ * ⁵⁵ - 56 991/11

BejSpJeI ₁ A

Phytophthora test (tomato) / Protective solvent: 4.7 weight steep acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether

Water: 95.0 parts by weight *

The amount of active ingredient required for the desired active ingredient concentration in the spraying liquid is mixed with the stated amount of the solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned,

The plants are sprayed young tomato plants with 2 to 4 leaves to dripping wet, The plants remain for 24 hours at 20 C and a relative humidity of 70 % in the greenhouse. "The tomato plants are then inoculated with an aqueous spore suspension of Phytophthora infestans. The plants are placed in a humid chamber with 100% humidity and a temperature of 18 to 20 C.

After 5 days, the infection of tomato plants is determined. The obtained rating values are converted to percent infestation. 0 % means no infestation, 100 % means that the plants are completely infested. In this test, z. B * following compounds a very good effect, which is clearly superior to those of the known from the prior art compounds (A) and (B): Compounds according to Preparation Examples: 12, 1 and 10,

10.12.1980 .220358 -'56- 56 991/11

Example B

Phytophthora ~ Test (Tomato) / Systemic

Solvent: 4.7 parts by weight of acetone Dispersant: 0.3 part by weight of alkylaryl polyglycol

ether water: 95, Ό weight steep

The amount of active ingredient required for the desired concentration of active substance in the casting liquid is mixed with the stated amount of solvent and the concentrate is diluted with the stated amount of water which contains the additives mentioned.

In. Unit soil grown tomato plants with 2 to 4 leaves are poured with 10 ml of the casting liquid in the stated active ingredient concentration, based on 100 ml of soil _f .

The treated plants are inoculated after treatment with an aqueous spore suspension of Phytophthora infestans. The plants are placed in a humid chamber with a humidity of 100 % and a temperature of 18 to 20 ⁰ C. After 5 days, the infestation of the tomato plants is determined. The rating values obtained are converted to percent infestation. 0 % means no infestation, 100 % means that the plants are completely infested.

In this test, z. Example, the following compounds a very good effect, which is superior to that of the known from the prior art compound (B):

Compounds according to Preparation Examples: 12, 1, 2, 8 and 10.

22C - 57 Preparation Examples Q ' ^CH 3> r < ^CH 3 - ) 3! example 1 B) 58 (Method f ₂ ^H 5 CH - ^ C - (II Il - C - OCH: h ₂ τ o - CH

10.12.1980 56 991/11

In a solution of 18.4 g (0.0816 mol) of N- (2,6-XyIyI) ethylglycine methyl ester and a few drops of dimethylformamide in 80 ml of toluene is added dropwise at room temperature 13.3 g (0.122 mol) of methoxyacetyl chloride and stirred for 3 h at 80 ⁰ C, After cooling, the solution is diluted with ethyl acetate, washed with dilute hydrochloric acid, water and sodium bicarbonate solution, dried over sodium sulfate and evaporated. The residue is crystallized from ligroin. This gives 10.4 g (43.5% of theory) of N-methoxyacetyl ~ IN ~ (2,6 ~ xylyl) ~ ethylglycine-methylester of melting point 96-97 ⁰ C.

Preparation of the starting product

A mixture of 387.3 g (2.1 mol) of 2-bromobutyrate, 127.0 g (1.05 mol) of 2,6-xylidine, 12l, 8 g (2.1 mol) of potassium fluoride and 100 ml of dimethylformamide

10.12.1980 • 3 58 - 56 991/11

stirred under nitrogen for 39 h at 100 ⁰ C "" After cooling, the FiItrat is filtered, poured into water, the precipitated oil extracted with methylene chloride, the extract was washed with water, dried over sodium sulfate and evaporated. The residue is fractionated through a column in vacuo. This gives 112.0 g (48.3 % of theory) of N ~ (2,6 ~ xylyl) ~ ethylglycine methyl ester of boiling point 100 to 110 ° C / 0.9 mbar.

Example 2

(Method a)

Into a refluxing solution of 11.1 g (0.05 mol) of N- (2,6-xylyl) ethyl methyl, 7.9 g (0.1 mol) of pyridine and 1.2 g (0.01 Mol) 4 ~ dimethylaminopyridine are added in 35 min 18.4 g of pyrazol-1-yl-acetyl chloride hydrochloride (prepared from 0.1 mol of pyrazol-1 ~ ~ ~ l ~ acetic acid) and heated for 22 h under reflux. The reaction mixture is evaporated, the residue partitioned between ethyl acetate and 1 molar citric acid, the organic phase washed with 5% sodium hydroxide solution and water, dried over sodium sulfate and evaporated. The residue is crystallized from toluene / petroleum ether (1: 4). This gives 11.3 g (68.7 % of theory) of N- (pyrazol-1-yl-acetyl) -N- (2,6-xylyl) -ethylglycine methyl ester of melting point 113 to 115 ⁰ C,

10,12.1980

2 2 Q -3 5 .8 - ⁵⁹ - ⁵⁶

Preparation of the starting product

II / =, .Cl-C-Cf-L-NT χ HCl

To a suspension of 12.6 g (0.1 mol) of pyrazol-1-ylacetic acid in 40 ml of toluene is added dropwise a dimethylformamide and dropwise at 25 to 30 ⁰ C (ice cooling) 19.05 g (0.15 mol ) Oxalyl chloride too. After stirring for 17 h at room temperature, the product is filtered off with suction and the residue is evaporated twice with toluene. This gives 18.4 g of crude pyrazol-1-yl ~ acetyl chloride hydrochloride, which is used further without purification,

Example 3 CH ₃ ^C 2 ^H 5 O Il -C - OCH N * " ^CH 3 I CH "L - OH Il Q

(Method f)

In a solution of 61.1 g (0.19 mol) of N-acetoxyacetyl-N- (2,6-xylyl) -ethylglycine methyl ester in 200 ml of methanol is added dropwise at room temperature in 15 min, a solution of 21.3 g ( 0.38 mol) of powdered potassium hydroxide in 200 ml of methanol, stirred for 1 h at room temperature and 3.5 h at 50 ⁰ C, the reaction solution is evaporated, the aqueous solution of the residue extracted with ether, acidified with half-concentrated hydrochloric acid and extracted with ethyl acetate Das Extract is dried over sodium sulfate and evaporated.

10.12.1980 - 60 - 56 991/11

The residue is dissolved in 180 ml of methanol and, after the addition of 81.0 g (0.571 mol) of boron trifluoride etherate (48% strength), heated under reflux for 17 h. The reaction solution is poured into 1000 ml of 10% strength Natriumhydrogencarbona.t solution with ice cooling, extracted several times with methylene chloride , the extract is washed with water, dried over sodium sulfate and evaporated. This gives 48.1 g (90.6 % of theory) of N ~ hydroxyacetyl-N ~ (2,6 ~ xylyl) ~ ethylglycine ~ methyl ester of melting point 101 to 102 ⁰ C,

Example 4

^C 2 ^H 5

(Method e / 1)

In 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 CZ, 2, 2loctane in 150 ml of methylene chloride is added dropwise at 20 to 25 ° C (ice cooling) 11.5 g (0.1 mol) of methanesulfonyl chloride and stirred for 17 h at room temperature. The reaction solution is washed with water, with the above aqueous pyridine, with dilute hydrochloric acid and water, dried over sodium sulfate and evaporated. The residue is from ligroin / toluene (7: 2). crystallized. This gives 13.9 g (78.8 % of theory) of N-Methansulfonyloxyacetyl-N- (2,6-xylyl) -ethylglycinmethylester of melting point 92 ⁰ C,

10.12.1980 220358 - 61 - 56 991/11

Example 5

C «H_ O

PH

^and 3 GH -C - OCH ₃

(Method e / 2)

A mixture of 11.2 g (0.04 mol) of N-hydroxyacetyl-N ~ (2,6-xylyl) -ethyl glycine methyl ester (Example 3) and 13.8 g (0.16 mol) of 3,4-one is added dihydro-2H ~ pyran lmolarem with 4 ml etherischern hydrogen chloride and stirred for 23 h bsi room temperature, After dilution with Essigester is washed with sodium bicarbonate solution and water, dried over sodium sulfate, evaporated and aer oily residue on the oil pump of volatile impurities be "freed" , 14.4 g (99.2 % of theory) of N-Tetrahydropyranyloxyacetyl-N- (2,6-xylyl) -ethylglycin methyl ester as

20 oil with the refractive index n _Q = 1.4959.

In an analogous manner, the compounds of the general formula:

(I)

receive.

Ex.

^RJ

10 _β 12.1930 56 991/11

melting point

( ⁰ C) or refractive index

CH

CH.

CH.

  CH.

CH.

11 , CH, 12 ^CH 3 13 ^CH 3 14 3

6-CH

 6-CH,

6-CH, 6-CH, 6-CH,

6-CH ", 6-CH.

-CH ₂ -O-CH ₃

-CH ₂ -O-COCH

-CHCl _n

-CH ₂ -N

= ~ N

.CH ₂ SCH ₃

0 0 0

0 Ό 0

0 0

CH.

CH.

CH. CH.

CH.

CH.

CH. CH.

21

: 1.5417

21 R ng "' ^D : 1.5037

, 79 to 101 bis

141 to

n ^ ¹ ' ⁵ : 1,4865

107

66 to

: 1.5470

Claims (4)

invention claim R represents alkyl, hydroxyalkyl, cyanoalkyl, alkenyl, alkynyl, H _a logenalkyl, cycloalkyl, cycloalkylalkyl, alkoxyalkyl, alkoxyalkoxyalkyl, acyloxyalkyl, alkylthioalkyl, alkylsulphinylalkyl, alkylsulphonylalkyl, dialkylaminoalkyl or optionally substituted aralkyl, R represents hydrogen "alkyl, alkoxy or H _a is lie, R is hydrogen, alkyl, alkoxy or halogen, R 1 is hydrogen or alkyl, Y 2 is oxygen or sulfur, R 1 is furyl, tetrahydrofuryl, thienyl, tetrahydrothienyl; optionally substituted by alkyl isoxazolyl; hydroxyalkyl; optionally cyano or thiocyano substituted alkyl, alkenyl, and alkynyl; cycloalkyl; dihaloalkyl; and the moieties -CH ₂ -Az, ^ CH ₂ -OR ⁵ , -CH ₂ -SR ⁵ , -OR ⁵ , -SR ⁵ _s -CH ₂ -OSO ₂ R ⁵ , -CH ₂ OCOR ⁵ , and -CH ₂ -O- (TN stands, where 56 991 11 .B / is optionally substituted alkyl, alkenyl, _s alkynyl and alkoxyalkyl, and Az is pyrazol-1-yl, 1,2,4-triazol-1-yl and imidazol-1-yl, in addition to extenders and / or surface-active agents. 2. A method of combating fungi, characterized in that U, N-substituted ethylglycine (thiol) ester of formula I is allowed to act on fungi or their habitat * Use of H, IT-disubstituted ethylglycine (thiol) esters of the formula I, characterized in that they are used for combating fungi. 4. A process for the preparation of fungicidal agents, which comprises mixing U, H-disubstituted ethylglycine (thiol) esters of the formula I with extenders and / _or the surface-active agents.