CA2191999A1

CA2191999A1 - Carbamoyl carboxylic acid hydrazides and their use against fungi

Info

Publication number: CA2191999A1
Application number: CA002191999A
Authority: CA
Inventors: Oliver Wagner; Frank Wetterich; Karl Eicken; Eberhard Ammermann; Gisela Lorenz; Thomas Muller; John-Bryan Speakman
Original assignee: Individual
Current assignee: BASF SE
Priority date: 1994-06-03
Filing date: 1995-05-20
Publication date: 1995-12-14
Also published as: KR970703306A; JPH10501215A; IL113916A0; AU685957B2; EP0763014A1; AU2735395A; BR9507914A; WO1995033710A1

Abstract

Disclosed are carbamoyl carboxylic acid hydrazides (I) and their salts, wherein: R1 is optionally substitued alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, aryl or heteroaryl or an optionally substituted non-aromatic carbo- or heterocycle, W1W2C=N-, where W1 is optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, aryl or heteroaryl and W2 is hydrogen or W1; R2 is hydrogen or optionally halogenated alkyl or cycloalkyl; R3 is optionally substituted alkyl, cycloalkyl or phenylalkyl; R4 is hydrogen or one of the R3 radicals, or R3 and R4 together with the C atom to which they are bound form an optionally substituted saturated carbo- or heterocycle; R5 is one of the R2 radicals; R6 is optionally substituted alkyl, alkenyl, alkinyl, cycloalkyl, cycloalkenyl, aryl or heteroaryl, an optionally sustituted non-aromatic carbo- or heterocycle or, when R3 = isopropyl, hydrogen; R7 is one of the R6 radicals except hydrogen; X1, X2 and X3 are in each case oxygen or sulfur. Disclosed also are methods for their preparation, agents that contain them, their use and intermediate products (IV), wherein X3 is oxygen and R3 is a CH(CH3)2, CH2CH(CH3)2 or CH(CH3)C2H5 group.

Description

005~/44896 The present invention relates to carbamoylu~Lbol,~dLazides of the 5 general formula I

x2 R2 ~2 X3 Rs ~6 Rl - ,'.' C - ~ - C - C - N - N - R7 ~4 15 and their salts, where the radicals have the following meanings:

Rl is Cl-C8-alkyl, C2-C9-alkenyl or C2-C8-alkynyl, it being pos-sible for these radicals to be partly or completely halogenated and~or to carry one to three of the following groups: cyano, Cl-C4-alkoxy, Cl-C4- h~ln~lkn~y~ Cl-C4 - alkyl-thio, Cl-C4-alku~y~aLbullyl~ C3-Ct-cycloalkyl, C3--C7--cyclo-alkenyl, aryl, aryloxy and heteroaryl, it being possible for the cyclic radicals in turn to carry one to three of the fol-lowing substituents: halogen, cyano, Cl-C4-alkyl, C1-C~-alk-oxyalkyl, Cl-C4-haloalkyl, Cl-C~-alkoxy, C1-C4-h~lo~l~nRy, C1-C4-alkylthio, Cl-C4-alku~y~dLLu..ylr aryl, aryloxy and heteroaryl, C3 - C~ - cycloalkyl or C3-C7-cycloalkenyl, it being po3sible for these radicals to be partly or completely h~log~nRt~d and/or to carry one to three ot the ~ollowing groups: cyano, Cl-C4-alkyl, Cl-C~-alkoxyalkyl, Cl-C4-haloalkyl, cl-C4-alkoxy, Cl - C4 ~-ln~lkn~y~ CL-C4-alkylthio, C1-C4-alku~yu,lLLu~lyl, aryl, aryloxy and aryl-(Cl-C4)-alkyl, it being possible for the cyclic groups to carry one to three of the following sub-stituents: halogen, cyano, C~-C~-alkyl, Cl-C~-alkoxyalkyl, Cl-C~-haloalkyl, C1-C~-alkoxy, Cl-C4-h~lo~l~oxy, Cl-C4-alkyl-thio, Cl-C4-alkoxycarbonyl, aryl and aryloxy, gO a nvn ~L~ ' ir' 4- to 8 ~d ring, which, as ring members, in addition to carbon can also contain one or two of the he~oat~ oxyqen, sulfur and nitrogen, it being possible for the carbon atoms in the ring to carry one or two of the follow;nq groups: halogen, cyano, Cl-C4-alkyl, Cl-C4-alkoxy-~5 alkyl, Cl-C4-haloalkyl, Cl - C4 lkoxy, Cl - C4 - h~1n~1knRyr Cl-C4-alkylthio, Cl-C4-alku~y~Lbu-.yl, aryl and aryloxy and ~ 0050~44896 219199~

the second and each further nitrogen atom as a heteroatom in ~ the ring carrying hydrogen or a Cl-C4-alkyl group, aryl or heteroaryl, it being possible for these radicals to carry one to three of the following groups: halogen, cyano, Cl-C~-alkyl, Cl-Cc-~qlkoxyalkyl, cl-c~ qlkyl~ C1-C~-alkoxy, ~ Cl-C~-hqlnalk~Yy, Cl-C4-alkylthio, Cl- Cq -alku~y-~-Lo.. yl, aryl, aryloxy and heteroaryl, in which the cyclic substituents in turn can carry one to three of the following substituents:
lo halogen, cyano, C1-C~ alkyl, Cl-C~-alkoxyalkyl, C1-C4-halo-alkyl, Cl-C~-alkoxy, Cl-c4-h~lo~lk~Ty~ Cl-C4-alkylthio and Cl-C4-alku~y~Lbv..yl or WlW2C=N-, where Wl is Cl-C8-alkyl which can be partly or ~ ly halo-genated and/or can carry one to three of the following groups: cyano, Cl-C~-alkoxy, Cl-c4-hql~l k~Yy~
C1-C4-alkylthio, aryl, aryloxy and heteroaryl, it being zo possible for the cyclic groups in turn to carry one to three o~ the following substituents: halogen, cyano, Cl - C4 - alkyl, CL - Cq - d1kOXYa1kY1, Cl - C~ ~-1 oqlkyl, Cl-C4-alkoxy, Cl-c4-halnAlk~yy~ C1-Cq-alkylthio, C1-C4-alkoxy~Lbu.,yl, aryl and aryloxy, C2-C~ alkenyl or C2-C~-alkynyl, it being possible for these radicals to be partly or completely halogenated and/or to carry one to three of the following groups:
cyano, C1-Cc-alkoxy~ C1-C4-hqlo-qlk~y, C1-Cq-Rlkylthio, C1-C4 alkù~y~Lbu~yl~ aryl and aryloxy, it being possible for the cyclic groups in turn to carry one to three of the following substituents: halogen, cyano, C1-C4-alkoxy, Cl--C~--h~lo~ Yy, Cl-C4--alkylthio,Cl--C4--alkoxycarbonyl, aryl and aryloxy, C~-C7-cycloalkyl or C3-C~-cycloalkenyl, it being possible for these radicals to carry one to three of the following groups: halogen, cyano, C~ - C4 - alkyl, C1-C4-alkoxyalkyl, Cl-c4-haloalkyl~ C1-C4-alkoxy, Cl-C4-ha~ k~y, C1-C~-alkylthio, C1-C4-alku~cdrbu-,yl, aryl and aryl-(cl-c4)-alkyl~ it being possible for the groups which contain aryl to carry one to three o~ the following substituents: halogen, cyano, Cl-c~-alkyl, Cl-C4-alkoxy-alkyl, C1-C4-haloalkyl, Cl-C4-alkoxy, C1-C4- h~ln~lk~y~
C1- Cq -alkylthio, C1-4-alkoxycarbonyl, aryl and aryloxy or ' ' o~50/44896 2 1 9 1 9 ~ 9 ~ 3 ~ryl or heteroaryl, it being possible for these radicals to carry one to three of the following groups: halogen, cyano, Cl-C4-alkyl, Cl-C4-alkoxyalkyl, Cl-C4-haloalkyl, Cl-C~-alkoxy, Cl-c4-h~ln~lknyy~ C1-C4-alkylthio, Cl-C~-alhu~r.aL~ullyl, aryl and aryloxy and W2 is hydrogen or one of the groups Wl;

R2 is hydrogen or Cl-C8-alkyl or C3-C7-cycloalkyl, which can be partly or ~ _letP1y h~ n~t~;

R3 is Cl-C8-alkyl, it being pos3ible for this radical to carry one to three of the following groups: halogen, cyano, Cl-C4-alkoxy, C1-C4-h~ knYy~ C1-C4-alkylthio and 1~ C1-C4-alhu~calL~

C3-C7-cycloalkyl or phenyl-(Cl-C4)-alkyl, it being possible for the rings of these radicals to carry one to three of the following groups: halogen, cyano, Cl-c~-alkyl, Cl-C4-alkoxy-ZO alkyl, Cl-C~-haloalkyl, Cl-C~-alkoxy, Cl-C4-haloalkoxy, Cl-C4-alkylthio, Cl-C~-alku~y~Lb~n~l, aryl and aryloxy;

R4 is hydrogen or one of the radicals R3 or ZS R3 and R4, together with the C atom to which they are bonded, are a 4- to 8- ~d ring which, as ring members, in addition to carbon can also contain one or two of the heteroatoms oxygen, sulfur and nitrogen, it being possible for the carbon atoms in the ring to carry one or two of the following groups: halogen, cyano, Cl-C4-alkyl, Cl-C4-alkoxy-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4- halo~lknxy~
Cl-C4-alkylthio, Cl-C~-~lkoxycarbonyl, aryl and aryloxy and nitrogen as a heteroatom carrying hydrogen or a C1-C4-alkyl group;
R5 is one of the radicals R2;

R6 is Cl-C8-alkyl, C2-C8-alkenyl or C2-C8-alkynyl, it being pos-sible for these radials to be partly or completely halo-genated and/or to carry one to three of the following groups:cyano, Cl-C4-alkoxy, Cl-C~-h~lo~lknxy, Cl-C4-alkylthio, C3-C7-oycloalkyl, C3-C7-cycloalkenyl, aryl, arylaxy and heteroaryl, it being possible for the cyclic radicals in turn to carry one to t!-ree of the following substituents: halogen, cyano, Cl-C4-alkyl, Cl-C4-alkoxyalkyl, C1-C4-haloalkyl, , . _ . .. _ _ . . _ .. ... .. ... . _ _ _ _ _ . _ ~- 0o5of44896 2 1 9 1 9 9 ~
.

Cl-C~-alkoxy, Cl-C4-h~loAlkrYy~ Cl-Cq alkylthio, aryl, aryloxy and h~ vhLlrl, C3 - C7 - cycloalkyl or C3-C7-cycloalkenyl, it being possible for S these radicals to be partly or completely halogenated andJor to carry one to three of the ~ollowing groups: oyano, Cl-C~ alkyl, Cl-C4-alkoxyalkyl, Cl-C4-haloalkyl, C1-C~-alkoxy, Cl-C~ h ln-l~nYy~ Cl-C4-alkylthio, aryl, aryloxy and aryl-(Cl-C~)-alkyl, it being possibLe for the cyclic groups to carry one to three of the following substituents: halogen, cyano, Cl--C4--alkyl,Cl-C4--alkoxyalkyl,Cl--C4--haloalkyl, Cl-C~-alkoxy, Cl-C4-h~oAlkn~y, Cl-C4-alkylthio, aryl and aryloxy, a non-aromatic 4- to 8 ~ ed ring, which, as ring members, in addition to carbon can also contain one or two of the heLe.~a~ oxygen, sulfur and nitrogen, it being possible for the carbon atoms in the ring to carry one or two of the following groups halogen, cyano, C1-Ci-alkyl, Cl-C4-alkoxy-alkyl, Cl-C4-haloalkyl, C1-C4-alkoxy, Cl - C4 - h~ 1 nR ~ koxy, Cl-C~-alkylthio,'aryl and aryloxy and the second and each fur-ther nitrogen atom as a heteroatom in the ring carrying hydrogen or a Cl-C~-alkyl group, aryl or heteroaryl, it being possible for these radicals to carry one to three of the following groups: halogen, cyano, Cl-C4-alkyl, Cl-C4-alkcxyalkyl, C1-C~-haloalkyl, Cl-C4-alkoxy, Cl-C~-h-lo~l~nYy, Cl-C4-alkylthio, aryl, aryloxy and hetero-aryl, in which the cyclic substituents in turn can carry one to three of the following substituents: halogen, cyano, Cl-C~-alkyl, C1-C4-alkoxyalkyl, Cl-C4-haloalkyl, Cl-C~-alkoxy, Cl - C4 - h~lr)~lknyy and Cl-C4-alkylthio or if R3 is isopropyl, hydrogen;
R7 is one of the radicals R6, excluding hydrogen;

Xl is oxygen or sulfur, X2 i5 oxygen or sulfur, 40 X3 is oxygen or ~ulfur;

e rr~lnrling the . ~ ds according to the following definition of the radicals:

45 Ia-d ~Rl = Ph-CH2; R2 = ~; R3 = C~3, (c~2l2c~3r c~(C~3)2 or Ph--CE~2; R4,Rs = }~: R5,R7 = CE~2CE~zCl) ~

, . . , _ ~ 00~0~44896 2 1 9 1 9 g ~

~ 5 Ie-h ~Rl = C(CH333; R2 5 H; R3 = CH3, CH(CH3)2, CH(CH3)CH2CH3, CH2CH(CH3)2 or Ph-CH2; R4,R5 = H; R6,R7 = CR2CH2Br), Ii tRI 5 Ph-CH2; R2 = H; R3 = CB3; R4,RS - H; R6 = CH3; R7 =
Ph), 5 Ij-k (Rl = Ph-CH2; RZ = H; R3 = CH(CH3)~ or CHlCH(C~3)2; R~,R5 =
H; R5,R7 ~ Ph), Il (Rl = C(CH3)3; R2 = H; R3 = CH(CH3)2; R4,R5,R6 5 H; R7 =
Ph), -Im (Rl = Ph-CM2; R2 = ~; R3 s Ph-C~2; R4, R5 = H; R5,R7 =
C112CH3 ) ~
In o (RL = Ph-CH2; R2 = N; R3 ~ CH25CH3 or CH2CH2SCM3; R4,Rs =
11; Rs,R7 = CH2CH2Cl).

The invention additionally relates to ~L~cs3a3 for preparing the 15 ~ _..ds } and their salts, compositions containing these sub-stances, and a method for controlling harmful fungi and the use of these substances therefor.

In addition, the present invention relates to amino acid hydra-20 zide i~ tes of the general formula IV

R3 X3 Rs R6 30 where X3 is oxygen and R3 is a group CH(CH3)2, CH2CH(CH3)2 or C~C~3)C2H5 and R4, R5, R6 and R7 have the meaning given in claim 1, ~Y~Iu~;ng the compounds according to the following definition of the radicals:

35 IVa-b (R3 = CH(CH3)2 or (CH2)2CH3; R4,Rs = H; R6,R7 = CH2CH2Cl), ~Vc-e (R3 = CH(CH3)2, CE(CH3)CH2CH3 or C~2CH(CH3)2; R4,Rs = H;
R6,R7 = CH2CH2Br), IVf (R3 ~ C~tCH3)2; R4,R5,R6 = H; R7 = Ph), IVg (R3 = CH(CH3)2; R4,R5 = H; R5,R7 = Ph).
~0 Compositions are known from D~-B 1 l9g 5~0 which contain alkyl-caLLol-~d~zideq, eg. the compound of the following formula ~ 0050/44896 o H2-c~-c~2 l NH--N~
s and which have an action against powdery mildew fungi.

JP - A 69/27 997 additionally describes the use of 4-methoxy-10 carbcnylterephthalic hydrazide or terephthalic bishydrazide fcr controlling rice blast.
However, these agents are still not satisfactory as fnn7ic~ s.

15 Further ~Lboh~v'Lazides are additionally known from the litera-ture; nothing has been repcrted, however, of a fnntJi~idal action of these ~ ,u~-ds (cf. Pharmazie 44, ~1988) page 608 to page 611; Pharmezie 44, (1989) page 316 to page 317; J. Org. Chem 36, (1971) page 1580 to page 1584; Farm~ Pol. 28, (1972) page 615;
20 EP-a 361 977; Collect. Czech. Ccmmun. 49, (1989) page 2551 tc page 2561).

It is an object of the present invention to provide novel carbamoylcarbohydrazides having improved action against harmful 25 fungi.
we have found that this object is achieved by the ~, ~ 'z I and their salts described at the cutset.
30 FULtl1 U, we have found i vL~an~ intermediates of the general formula rv ~or preparing these substances.
we have additionally found compositions containing them, pro-cesses for preparing the c ~,v~..d~ I and their salts and the com-35 pcsitions containing them and in addition a process for control-ling harmful fungi and the use of the c _ '~ I and their salts therefor.

~he c ~u--~s I and their salts can be prepared starting from the 40 uuLL~a~uu..ding carbamoylcarboxylic acids II. Preferably, they are obtained by the yLu~ S A, B and C described in the fcllowing tthe ~ouben-Weyl refer~nces relate to: Buu'v~l~ t7_yl~ Methoden der org~n;c~h~n Chemie (Methcds of Organic Chemistry), 4th editicn, Thieme Verlag, Stuttgart).
4~

- ' 2i91993 t Process A

The carbamoyl~L~L~d~zides I are obtained by reacting the carbamoylcarboxylic acids II with the hydrazines III.
s X7 R2 R3 X3 Rs Rs Il l l 11 1 1 Rl--Xl--C--N--C --C--011 + Ei--N-- N -- R7 ~

II III

X2 ~2 R3 X3 Rs R6 Rl--xl--C--N--C --C--N-- N--R7 I

The carbamoylcarboxylic acids II are known or obtainable by known methods, r~peri~l7y starting from the amino acids on which they are based ~cf~, for example, n~ubell~eyl UMethoden der organi-schen Chemie~ [Methods o~ Organic Chemistryl, Volume I5/1, 4th 25 Edition, Thieme Verlag Stuttgart 1977; 3P 53148530; JP 52151146;
J. Org. Chem. 43 11978], 2g30-2932; J. Chem. Soc., Perkin Trans 1, 1972, 1983-1985; Chem. Ber. 104 tl971], 31S6-3167; J. Org.
Chem. 36 [19711, 49-59; ~elv. Chim. Acta 52 [1969], 282-291;
Tetrahedron 34 11978], 2763-2766; Chem. Pharm. Bull. 19 [1971], 30 912-929, 3. Chem. Soc. 1952, 2076-2079~.

The hydrazines III are likewise known or easily obtainable (cf.
nouben-Weyl, volume 10~2, page 1 to page 71 and page 169 to page 409, ~p~riAlly page 396 to page 399 and page 402 to page 405).
This process A is preferably carried out by first converting the carbamoylcarboxylic acids II to carboxyl-activated derivatives, esperi~lly to acyl cyanides or anhydrides (cf. PharmaZie 4~, (1989) page 316 to page 317 and page 608 to page 611; Tetrahedron 40 Letters, volume 18, (1973) page 1595 to page 1598 and ~ouben-~eyl, volume 15/1, page 28 to page 32). These derivatives are then reacted with the hydrazines III in the presence of bases.

~ 0050~44896 2~91~99 A suitable reaction for preparitg the carboxyl-activated acyl-cyanides is eg. the reaction of the carbamoylcarboxylic acids II
with diethyl ~y~ r~ h~n~te~ Pcp~ lly in an inert solvent such as tetral.~lLuCuLdll, toluene or dichloromethane.

To prepare the carboxyl-activated anhydrides, the reaction of the carbamoylcarboxylic acids II with carbonyl ~hl~rid~c such as iso-butyl chluLvCuL~.~Le in the presence of bases and in the presence or absence of an inert solvent such as toluene or tetraLyd 10 is preferred.

The reaction of the hydrazines III wlth the carboxyl-activated carbamoyloarboxylic acids II is preferably carried out in a sol-vent such as dichloromethane, tetrahydLuruLdn or toluene.
In particuiar, the bases used can be the hydrazines III them-selves, the bases customarily being L~u~ td from the crude product.

20 In a preferred -'i L of this stage of the process, the carbamoylcarboxylic acid II, the hydrazine III, the reagent suitable for generating the carboxyl-activated derivative o~ the carbamoylcarboxylic acid II and the base are reacted in a one-eot process, if appropriate in an inert solvent, and the crude 25 product is then worked up to the carbamoylcaLbGI.yl~zide I in a manner known per se.

Process B

30 The carbamoylcarbohydrazides I, in which Rl is a group -WIW2C=N-, are also obtained by converting the carbamoyLudLbol-ydLdzides I, in which Xl, x2 and X3 are in each case oxygen, and the group RL-Xl-(CO) is a protective group which can be removed in a manner known per se, to carbohydrazides IV and reacting these with chlo-35 roformyl oximes V in the presence of bases.

Stage ~a: Preparation of the carbohydrazides IV

't ooSOf44896 219199~

XZ R2 R3 X3 R5 ~6 Il I I 11 1 1 ~
R1 - Xl - C - N - C - C - W - N - R7 I

R2 R3 X3 R~ R6 ~ - N - f - C - N - N - R7 IV
15 The removal of the group Rl-XL-~C0) from the carbamoylcarbohydra-zides I can be carried out in a manner known per se (cf ~ouben-Weyl, volume 15/1, page 46 to page 305, ~cpe~iAlly page 126 to page 129; Pharmazie 4~, (1989) page 316 to page 317).

20 Suitable removable groups r~cpr?~;~lly contain the tert-butyl group znd additionally the benzyl group as a radical R1.

If R1 = LeL~ bu8yl, for example, removal ~as~ rily takes place by reaction with an acid, in particular a protic acid such as 25 hydrochloric acid, hYdLUb1~ r' acid or trifluoroacetic acid (loc.
cit.).
~he carbamoylcarbohydrazides I suitable as ~tarting substances are obtainable by known ~LVU~55eS (cf. Pharmazie 44, ~1989) page 30 316 to page 317 and page 608 ~o page 611; ~ouben-Weyl, volume 15Jl, page 28 to page 32~ or in particular by process A according to the invention.

Stage Bb: Preparation of the carbamoylcaL'vGl.~dLdzides I

~191999 ~ 10 wl O R2 R3 X3 R5 R6 li I 1 11 1 ~
C=~--O--C - Cl I H - ~ - f _ c _ N - N - R7 -w7 R~
v IV

Wl o R2 ~3 X3 Rs R6 C=~ - o - C - N - C - C - N - N - R7 w2 lS
The carbohydrazides IV resulting ~rom the synthesis stage 13a) are reacted ~ith the chloroformyl oximes V in the presence of bases.

20 The chloroformyl oximes V are known or obtainable by known pro-cesses, eg. by phosgenation of oximes (cf. Z. Chem. 9, (19671 page 344 to page 3451.

The reaction is preferably carried out in an organic solvent, 25 ~speciAlly in toluene, methylene chloride, tetral.~d VfUl-l~ or mi~tures of these.

suitable bases are equally inorganic and organic bases, organic bases and, among these in turn, tertiary amines such as triethyl-30 amine, pyridine and N-methylpiperidine being preferred.

As a rule, the reaction is carried out at from -40 to 50 C, pre-ferably from -10 to 20-C.
35 The carrying-out of this reaction is otherwise famiLiar to the person skilled in the art, so no further explanations are needed (c~. ~ouben-Weyl, volume lS/I, page 117 to page 125; ~ev.
Endocrinol. 13 (11_~L~L~v~h~eal Pept. norm. Other 3iol. Act-Pept.1, (19811 page 37 to page 47).
Process C

The carbamoylcarbohydrazides o~ the general formula I according to claim 1, in which R6 is C~-C8-alkyl, C4-C7-cycloalkyl or ~5 aryl-(Cl-C4)-alkyl, are also obtainable by reacting carbamoyl-carbohydrazides of the general formula I according to claim 1, in which R6 is hydrogen, with a compound of the general formula R6-X

; OoSoJ4~896 ~ ' ~ 1 9 ~ 11 in which R6 is Cl-Ca--alkyl,C4-C7-cycloalkyl or aryl-(C1-C~)-alkyl and X is a negative leaving group, with additional use of a base.

The carbamoyl~a-LvllylL~zides of the general formula I, in which ~6 5 is hydrogen, are ~h~lin~hlo in a manner known per se ~cf.
D~-A 1 089 390; zh. Org. Khim. 14 (1978), page 1086), or in par-ticular by process a according to the invention.

A suitable negative leaving group X ifi the methylsulfonyl or the 10 4-methylphenylsulfonyl anion and preferably halide anions such as iodide and in particular chloride and bromide.

The bases used are ~po~i~lly alkali metal carbonates and ~ Y;~~ such as sodium o~rbnn~o, 30dium methoxide and sodium 15 ethoxide, in addition alkaline earth metal carbonates such as calcium carbonate, alkali metal or alkaline earth metal hydroxides, eg. 60dium hydroxide and calcium hydroxide, hydrides, eg. sodium hydride, hydluJ-~ tes, eg. sodium hydrogen-carbonate, alkanes, eg. n-butyllithium, or tertiary amines such 20 as triethylamine.

The reaction can be carried out without solvent or in a solvent which is inert under the reaction conditions, such as dimethyl-f~rr~ o, tetrallyJLvfuL~n~ hl. ~hane or alkanols such as 25 methanol or ethanol.

As a rule, the reaction is carried out at from 10 to 60 C and under a; ~ ic pressure.

30 Other~ise, the process is carried out in a manner known per se (cf. ~30uben-Weyl, volume 10/2, page 402 to page 40~).

The reaction mixtures obtained by pLv~e~es A, B and C are customarily worked up to the c _ ~- I in the customary manner, 35 eg. by mixing with water, separating the phases and, if neces-sary, purifying the crude products by ~ LOYL~PI.Y~ The inter-mediates and final products are obtained in some cases in the form of cnl~r30ss or slightly brownish, viscous oils whioh can be freed from the volatiLe , Ls under reduced pressure and at 40 moderately elevated ~ ~ULe. If the Llt ~-~tes and final products are obtained as solids, they can also be purified, for example, by recrystallizing or digesting.

4'i 0050/~4896 - 2 1 9 1 9 ~ ~

Depending on the nature of the substituents, the ~ ' of the ~ormula I can, if approeriate, be present as ge~metrical and/or optical isomers or isomer mixtures. ~oth the pure isomers and the mixtures of the isomers have fnn~ir;f~l action.

The salts are also part of the invention, in particular of the acid-stable c _ '- } which contain basic centers, f~pff~;~lly ba~3ic nitrogen atoms, ie. in particular the salts with mineral acids such as sul~uric acid and plos~hvLic acid or Lewis acids 10 such as zinc chloride. Customarily, the nature of the salts does not matter. In the context of the invention, those salts are pre-ferred which do not damage the plants, sur~aces, materials or spaces to be kept free o~ harmful fungi and do not adversely affect the action of the ~ , ' I.
The salts of the ~ ,ds I are ~f~ csih]e in a manner known per se, espef~i~lly by reacting the CULLI~ ;ng carbamoylcarbo-hydrazides I with said acids in water or an inert organic solvent at from -30 to 120 C, preferably from 0 to 60'C.
In the preparation o~ the carbamoylcaLb~hydL~zides I according to process B, there are also cbtained novel int -i~t~c of the general formula IV

~.3 X3 E~.S R6 Il l I
~2~ C - N - N - R7 IV
~4 where X3 is oxygen and R4, R5, R6, and R7 have the meanings given in claim 1 and R1 is a group C~( C~3 ) 2 ~ CH2C~ ~ C~3 ) 2 or C~( C~3 ) C2~5 ~
35 the ~ ~ according to the following definition of the radi-cals already being known:

IVa-b (R3 = C~(CR3)2 or (C~212C~3; R4,Rs = ~; R5,R7 = C~zC~2Cl), IVc-e (R3 = C~(C~3)2, C~(c~3lC~2C~3 or CH2c~(cs3)2; R~,R5 = H;
R6,R7 - C~2C82~r), IVf (R3 = C~(C~3)2; R~,R5,R6 = ~; R7 = Ph), IVg (R3 = CH(C~3)2; R~,R5 = ~; R6,R7 = Ph) 0050J44896 2 1 9 1 ~ ~ ~

~ 13 (cf. Pharmazie, 44, (1989) page 608 to page 611; Pharmazie, 44, (1989) page 316 to page 317; EP-A 0 361 977; Int. J. Pept.
Protein Res. 21 (19B3) page 406; ~arm. Pol. 28, (1972) page 615 to page 619).
s Among the novel amino acid hydrazides IV, those are preferred in which R3 is a group CH(C~3)2, R4 and R5 have the meanings given in claim 1, lo R6 is Cl-C8-alkyl, it being possible for this radical to be partly or completely hAlng~nA~d and/or to carry one to three of the following groups: cyano, C1-C4-alkoxy, C1-C~-halo-alkoxy, Cl--Cj--alkylthio,C3--C7--cycloalkyl,C3--C7--cycloalkenyl, aryl, aryloxy and heteroaryl, it being possible for the cyclic radicals in turn to carry one to three of the following substituents: halogen, cyano, C1-C4 alkyl, C1-C~-alkoxyalkyl, Cl- C4 ~lnAlkyl~ C1-C4-alkoxy, Cl-C~-halo-alkoxy and C1-C~ alkylthio, aryl, aryloxy and heteroaryl and 20 R7 is aryl, it being possible for this radical to carry one to three of the following groups: halogen, cyano, C1-C4-alkyl, Cl - C4 alkoxyalkyl, C1-C4-haloalkyl, C1- C4 alkoxy, C1-C4-halo-alkoxy, C1-C4-alkyl~hio, aryl, aryloxy and heteroaryl, in which the cyclic substituents in turn can carry one to three 25 of the following substituentsl: halogen, cyano, C1-C~-alkyl, Cl-C~-alkoxyalkyl, C1-4 -haloalkyl, Cl-C4 alkoxy, Cl-C4-halo-alkoxy and Cl-C~-allcylthio.

~ith respect to their use for preparing carbamoylcarbohydra-30 zides I, the : ~- IV compiled in the following tables are particularly preferred.
Table 1 C\ / C~3 C~ ~ R5 R6 l l 11 1 1 ~ - N - C - C - ~ - N - R7 ~o. Rs R5 R7 45 1 ~ C~3 C6~5 2 ~} Ci~3 4--Cl--C6Ei4 3 H c~3 4-c~3-c6~q 0050,4~896 2i9~9~
.

~o. R~ R~ R7 4 B CH3 4-OCH3-c6H4 H CH3 3,4-(0CH3)2-C6H3 5 6 C1i3 CH3 4-cl-c6H4 8 H CH3 4-Cl-C6Bq H CH(CH3)2 CH2-(4-Cl-C6H4) 11 H CH~CH3)2 4-Cl 12 B CR~CH312 cH(c6Hs)(4-cl-c6H4) 13 H Cn(CH3l2 4-cl-cGH4 14 c~3 CH(CH312 4-CB3-C6H~
H CH(CH3)2 4-OCH3-C6H4 15 16 H CH(CH3)z 3~4-(ocH3)2-c6B3 17 H CH2CH3 CH2(4-Cl-C6H~) 18 B CH2CH3 CHCH3(4-Cl-C6H4) 19 H CH2CH3 cH(c6Hs)(4-cl-c6H4) 20 20 CH3 CH2CH3 4-Cl-C6B4 22 H CB2CH3 4_oCH3-C6H4 23 H CH2CR3 3~4-(ocH3)2-c6H3 H cyclc-CgHg CH2(4-cl-c6H~) H cyclo-C5Hg CH(CH3)(4-Cl-C6B4) 26 H cyclo-C5Hg CH(C6H5)(4-Cl-C6H4) 27 H cyclc-C5B9 4-C1-C6B4 2S B cycl~-C5H9 4--CB3--C6H4 29 H cyclr~-C5H9 4--0Ca3--C6H4 H cyclo-C5H9 3~4-(ocH3)2-c6H3 31 H cycl~-C6Hll CB2(4-cl-c6H4) 32 ~ cyclo-C6HIl CH(CH3)(4-Cl-C6H4) 35 33 B cyclo-C6Hll CB(C6Hs)(4-Cl-C6H4) 34 B cyclo-C6Hll 4--Cl--C6B4 H cycl~--C6H11 4--CB3--C6H4 36 H cyclo-C6Hll 4-OCB3-C6H4 40 37 H cyclo-C6Hll 3,4-(OCH3)2-C6H3 39 CH3 CH3 4-Cl-C6H4 CH3 CH3 4-CB3-C6H~
gl CH3 CH3 4-OCH3-C6~4 ~5 CH3 CH3 3,4-(OCH3)2-C6H3 0050~44896 ~ 21919~

~ 15 In the definition of the ~ ' ~ given at the outset, collec-tive terms were used which are L~lesa..~ative of the following substituents:
5 halogen: fluorine, chlorine, bromine and iodine;
alkyl: straight-chain or branched alkyl groups having 1 to 8 carbon atoms, eg. Cl-C6-alkyl such as methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl, lO l,1-dimethylethyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3_methylbutyl, l,l-dimethylpropyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, l-etllylpropyl, n-hexyl, l-methylpentyl, 2-methylpentyl, 3-methylpentyl, ~-methylpentyl, 1,1-dimethyl-butyl, 2,2-dimethylbutyl, 3,3-dimethylbutyl, l,2-dimethylbutyl, 15 1,3-dimethylbutyl, 2,3-dimethylbutyl, l-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1 othyl-l-methyl-propyl and 1 cthyl-2-methylpropyl;

haloalkyl or partly or ~ ~let~ly halogenated alkyl: straight-20 chain or branched alkyl groups having 1 to 4 or 8 carbon atoms (as mentioned above), it being possible in these groups for the hydrogen atoms to be partly or completely replaced by halogen atoms (as mentioned above), eg. Cl-C2-haloalkyl such as chloro-methyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoro-25 methyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoro-methyl, chlorodifluoromethyl, l-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-~1uoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl;
alkoxy: straight-chain or branched alkoxy groups having l to 4 carbon atoms, eg. Cl-C3-alkoxy such as methoxy, ethoxy, propoxy and l-methylethoxy;

35 alkoxyalkyl: straight-chain or branched alkyl groups having 1 to 8 carbon atoms (as mentioned above), which in any desired posi-tion carry a straight-chain or branched alkoxy group (as mentioned above) having, in the case of C~-C4-alkoxy, 1 to 4 carbon atoms, such as methoxymethyl, ethoxymethyl, n-propoxy-40 methyl, n-~Lv~ Ll-yl, 1-methoxyethyl, 2 '~ y~Lhyl, 1-ethoxy-ethyl, 2-ethoxyethyl, 2-n-y.u~u~Lhyl and 2-butoxyethyl;
bAl ~Al kn~y: straight-chain or branched alkoxy groups having 1 to 4 carbon atoms tas mentioned above~, it being possible in these g5 groups for the hydrogen atoms to be partly or completely replaced by halogen atoms (as mentioned above), eg. C1-C2-h~l~Alkn~y such as chluL~ ~hu~y, dichloL Lllu~y, trichlu-~ Lhu~y~ fluoro-00s0~44896 2 1 9 1 ~ 9 ~
.

16methoxy, diiluoromethoxy, trifluo.~ ~h~y, chloro~luoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-fluoroethoxy, 2-fluuLv~ yt 2,Z-difluulve~L~y, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-di~1uoroethoxy, 5 2,2-dichloro-2-~lu~.o~Lhu~y~ 2,2,2-trichlolceU.v~y and penta-f 1UVL V~ l.hu~y;

alkylthio: straight-chain or branched alkyl groups having 1 to 4 carbon atoms (as r ion~d above), which are bonded to the struc-10 ture via a suliur atom (-,S-), eg. Cl-C~-alkylthio such as methyl-thio, ethylthio, propylthio, 1-methylethylthio, n-butylthio and tert-butylthio;

alkoxycarbonyl: straight-chain or branched alkoxy groups haring 1 15 to 4 C atoms (as mentioned above), ~hich are bonded to the struc-ture via a carbonyl group (-C0-);
alkenyl: straight-chain or branched alkenyl groups having 2 to 8 carbon atoms and a double bond in any desired position, eg.
20 C2-C6-alkenyl such as ethenyl, l-prcpenyl, 2-propenyl, 1-methyl-ethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl r 2-methyl-2-propenyl, 2-methyl-1-prcpenyl, 1-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, l-methyl-l-butenyl, 2-methyl-1-butenyl, 25 3-methyl-1-butenyl, 1-methyl-Z-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methy1-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-prcpenyl, 1,2-dimethyl-2-propenyl, l-ethyl-l-propenyl, l-ethyl-2-propenyl, l-hexenyl, 2-hexenyl, 30 3-hexenyl, 4-hexenyl, 5-hexenyl, l-methyl-l-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methy1-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 35 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 40 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1 cthyl-l-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 45 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, l-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl-2-propenyl;

0050/g4896 17 2 1 ~ 1 ~ 9 ~

alkynyl: straight-chain or branched alkynyl groups having 2 to 8 carbon atoms and a triple bond in any desired position, eg.
C2-C6-alkynyl such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 5 2-pentynyL, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1 cthyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, S-hexynyl, 1-methyl-2-pentynyl, l-methyL-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 10 2-methyL-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methy1-2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1 ethyl-2-butynyl, 1-ethyl-3-butynyl, 2 ethyl-3-butynyl and I5 1-cthyl-1-methyl-2-propynyl;
cycloalkyl: monocyclic a7kyl groups having 3 to 7 carbon ~ing members, eg. C3-C7-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl;
2~
cycloalkenyl: monocyclic alkyl groups having 5 to 7 carbon ring members which contain one cr more double bonds, eg.
C5-C7-aycloalkenyl such as cyclopentenyl, cyclohexenyl and cyclo-heptenyl;
non-aromatic 4- to 8-membered rings, which, as ring members, in addition to carbon also contain one or two oxygen, sulfur or nitrogen atoms, such as saturated 5- or 6 r ~ ~d rings having 1 or 2 nitrogen and~or oxygen atoms such as 3-tetrahydLofuLduyl, 3~ l-piperidinyl, 2-piperidinyl, 3-piperidinyl, 4-piperidinyl, 2-tetrahydL~yyLdllyl~ 3-tetral.ydL~yyL~..yl~ 4-tetral.yd~yyLdnyl, 2-morpholinyL and 3-morpholinyl:

aryl: monocyclic or polycyclic aromatic groups having 6 to 10 35 carbon atoms, such as phenyl and naphthyl;

arylal~yl: aryl groups ~as mentioned above), which in the case of aryl-(Cl-C~)-alkyL are bonded to the ~ù~uLe via aLkyl groups having 1 to 4 carbon atoms (as mentioned above), eg.
40 phenyl-(CI-4)-alkyl such as benzyl, 2-phenylethyl, 3-phenyl-propyl, 4-phenylbutyl, 1-phenylethyl, 1-phenylpropyl and 1-phenylbutyl;

aryloxy: aryl groups (as mentioned above), which are bonded to 45 the ~LU~LuL~ via an oxygen atom (-o-), such as phenoxy, 1-naph-thoxy and 2-naphthoxy;

.. .. , .. , . , . , , . , . _ _ _ _ _ _ _ , .

~050~44896 ~ 1 9 1 ~ 9 9 .

Le~e~vaLyl: aromatic mono- or polycyclic radicals, which in addi-tion to carbon ring members can additionally contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and an oxygen or a sulfur atom or an oxygen or a sulfur atom, eg.:

- 5 ~_ .d heteroaryl, cnn~ining 1 to 3 nitrogen atoms:
5 - ' ed ring-heL~LvaLyl groups, which in addition to carbon atoms can contain 1 to 3 nitrogen atoms as ring members, eg. 2-pyrrolyl, 3-pyrrolyl, 3~pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-triazol-3-yl and 1,3,4-triazol-2-yl;

- s ed heteroaryl, con~;n;ng 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sul~ur atom or oxygen atom or 1 1~ oxygen or 1 sulfur atom: 5 ' -~d ring heteroaryl groups, which in addition to carbon atoms can contain 1 to 4 nitrogen atoms or I to 3 nitrogen atoms and 1 sulfur or oxygen atom or 1 oxygen or sulfur atom as riny members, eg. 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, S-isoxazolyl, 3-isothiazolyl, 4 - ifi othiazolyl, S-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, S-oxazolyl, 2-thia201yl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-S-yl, 1,2,4-thia-diazol-3-yl, 1~2~4-eh~ Ql-5-yl~ 1,2,4-triazol-3-yl, 1,3,4-ox~ 7nl-2-yl, 1~3~4-th;7~ nl-2 1,3,4-triazol-2-yl;

- benzo-fused S ~ L~d heteroaryl, containing 1 to 3 nitrogen atoms or 1 nitrogen atom and/or an oxygen or sulfur atom:
' ~el ring heteroaryl groups which in addition to carbon atoms can contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms and 1 sul~ur or oxygen atom or 1 oxygen or one sulfur atom as ~ing members, and in which 2 adjacent carbon ring members or 1 nitrogen and 1 adjacent carbon ring member can be bridged by a buta-1,3-diene-1,4-diyl group;

- 5 '- ed heteroaryl bonded via nitrogen, containing 1 to 4 nitrogen atoms, or benzo-fused 5 - ' ~d heteroaryl bonded via nitrogen, oontaininy 1 to 3 nitrogen atoms: 5 ~ ~d ring heteroaryl groups which, in addition to carbon atoms, can contain 1 to 4 nitrogen atoms or 1 to 3 nitrogen atoms a~
ring members, and in which 2 adjacent carbon ring members or one nitrogen and one adjacent carbon ring member can be bridged by a buta-1,3-diene-1,4-diyl group, these rings being bonded to the s~Lu~5ùLe via one of the nitr~gen ring members;

_ _ _ _ , . _ _, _ . _ . _ .... . .. . _ _ _ _ _ _ _ _ _ ~ 19 - 6 ed he~odl~l, contai~ing 1 to 3 or 1 to 4 nitrogen atoms: 6 ~ ~d ring heteroaryl groups which, in addition to carbon atoms, can contain 1 to 3 or l to 4 nitrogen atoms as ring members, eg. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl and 1,~,4,5-tetrazin-3-yl;

- ben~o Lused ~ ~d heteroaryl, con~aining 1 to 4 nitrogen atoms: 6 ~ ed ring heteroaryl groups, in which 2 ad~acent carbon ring members can be bridged by a buta-1,3-diene-1,4-diyl group, eg. quinoline, isoquinoline, ~n;n~70line and q.linn~lin~

15 ~he statement partly or l~ly halogenated is intended to express that in the groups characterized in this way the hydrogen atoms can be partly or completely replaced by identical or di~-ferent halogen atoms, as mentioned above.

20 with respect to their biological action against harmful fungi, I are preferred in which ~7 i5 C3-C7-cyoloalkyl or C3-C7-cycloalkenyl, it being possible for these radicals to be partly or completely halogenated and/or to carry one to three of the ~ollowing groups: cyano, C1-C4-alkyl, Cl-C4-alkcxyalkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-hAlo~ xy~ Cl-C4-alkylthio, aryl, aryloxy and aryl-(Cl-C4)-alkyl, it being possible for the cyclic groups to carry one to three of the ~ollowing substituents: halogen, cyano, Cl-C4-alkyl, Cl-C4-alkoxyalkyl, Cl-C4-haloalkyl, Cl-C4-alkoxy, Cl-C4-h~lo~lk~y, Cl-C4-alkylthio, aryl and aryloxy or R7 is a non-arcmatic 4- tc ~ _d ring which, as ring members, in additicn to carbon can also contain one or t~o of the heteroatoms oxygen, sulfur and nitrogen, it being pO8-sible for the carbon atom3 in the ring to carry one or two of the following groups: halogen, cyano, Cl-C4-alkyl, Cl--C4--alkoxyalkyl,Cl-C4--haloalkyl,Cl--C4--alkoxy,Cl--C4--halo-alkoxy, Cl-C4-alkylthio, aryl and arylo~y and the second and each ~urther nitrogen atom as a heteroatom in the ring carry-ing hydrogen or a C~-C4-alkyl group or ~7 is aryl or heteroaryl, it being possible for these radicals to carry cne tc three of the ~olLcwing groups: halogen, cyano, Cl-C4-alkyl, Cl-C4-alkoxyalkyl, Cl--C4--haloalkyl, C~-C4- alkoxy~ Cl-C4 ~Alo~lk~y~ C1-C~-alkylthio, aryl, aryloxy ~ 0050/44896 ~ 2191999 and heteroaryl, in which the cyclic substituents in turn can carry one to three of the following substituents: halogen, cyano, cl-C4-alkyl, Cl-C~-alkoxyalkyl, Cl-C~-haloalkyl, C1-C4-alkoxy, Cl-C4-h loalkr~y and CL_C4 - alkylthio.

Particularly ~Lefe.L~d . ~ I are those in which the radicals have the follcwing meanings, namely per se or in com-bination:

10 Rl i8 Cl-C6-alkyl, it being possible for this radical to carry one to three of the following groups: halogen, Cl-C~-~lkoxy, phenyl and phenoxy, ~sper;ally Cl-C4-alkyl and benzyl, Rl i9 C3-C7-cycloalkyl, it being possible for this radical to 1~ carry one to three of the following groups: halogen, C1-C4-alkoxyalkyl, phenyl and phenoxy and espe~iAlly cyclo-propyl, oyclopentyl and cyclohexyl, Rl is aryl, it being possible for this radical to carry one to three of the following groups: halogen, cl-C4-alkyl and C1-C4-alkoxy, especially phenyl and naphthyl, which can be unsubstituted and/or in turn can carry one to three of the following groups: fluorine, chlorine, bromine, Cl-C4-alkyl, methoxy, ethoxy, n-propoxy, iso~ o~y, n-butoxy and isobutoxy and ~eLL Lu~u~, and in particular unsubstituted phenyl, l-naphthyl and 2-naphthyl, R7 is hydrogen, 30 R3 is Cl-C6-alkyl, rsreriAlly Cl-C4-alkyl, R3 is C3-C6-cycloalkyl, especially cyclopropyl, cyclopentyl or cyclohexyl, 35 R4 is hydrogen, R4 is Cl-C~-alkyl, ~qperi~lly Cl-C~-alkyl, R4 i5 C3-C6-cycloalkyl, ~rerially cyclopropyl, cyclopentyl or cyclohexyl, R4 is hydrogen, R3 is Cl-C6-alkyl and R4 is hydrogen, RS is hydrogen, ; ' ooso/44896 2i919~9 R3 is C3-C6-cycloal~yl and R4 is hydrogen, Rs is Cl-4-alkyl, esp~ ly methyl or ethyl, 5 R5 is C3-C6-cycloalkyl, e~ci~lly cyclopropyl, R6 i8 Cl-Cs-al~yl, ~ r~ y methyl, ethyl, n-propyl or iso-propyl, 10 Rfi is C3-C~-cycloalkyl, ~6 is aryl, it being possible for this radical to be unsubsti-tuted or to carry one to three of the following groups: fluo-rine, chlorine, bromine, cyano, Cl-C4-alkyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, iso~L~uu~yr n-butoxy, isobutoxy, te~-Lu~u~y, trifluor~ ~h~y~ phenyl and phenoxy, R7 is phenyl, it being ~ossible for this radical to be unsubsti-tuted or to carry one to three of the following groups: fluo-rine, chlorine, bromine, cyano, Cl-C~-alkyl, trifluoromethyl, methoxy, ethoxy, n-propoxy, isu~uLU~uu~y~ n-butoxy, isobutoxy, teL~ ~u~u~y, trifluoromethoxy, phenyl and phenoxy, ~7 i5 naphthyl, it being possible for this radical to be unsub-z5 stituted or to carry one to three of the following groups:fluorine, chlorine, bromine, cyano, Cl-C~-alkyl, trifluoro-methyl, methoxy, ethoxy, n-propoxy, isu~Lu~U~y~ n-butoxy, isobutoxy, tert-butoxy, trifluoromethoxy, phenyl and phenoxy, ~0 R7 is C3-C7-cycloalkyl, it being possible for this radical to be unsubstituted or to carry one to three of the following groups: halogen, Cl-C4-alkyl and Cl-C~-alkoxy, especially sub-stituted C5-C7- and in particular C6-cycloalkyl of this type.

35 With regard to the meaning of Xl, x2 and X3, ~ __ ' I are par-ticularly ~Lef~LL~d where X', x2 and X3 are oxygen. I~ one or more of Xl, x2 and X3 are sul~ur, those ~ .ullds I are particularly preferred vhere Xl and x2 are sulfur, especially those where only xl is sulfur. Hovever, those '- I can also be preferred 40 where only x2 is sulfur The ~ __ ' I complled in the ~ollowing tables are very particularly preferred wi~h respect to their use.

0050/44'.896 ~.~ 22 - 21919~
Table 2 ~ H R3 0 Rs Rc Rl--Xl _ C ~ C --C--U -- tl --R7 %1 is oxygen or ~3ul~ur.
No. Rl R3 RS R6 R7 C(C53)3 Cd(CH3)2 CH3 CH3 c6~s 15 2 C(CN3 3 Cl7(CH3)C2ll5 H CH3 C6715 3 C CN3 3 CH2cH(cH3l2 N CH3 C6H5 4 C'CH313 C!l(CH3)2 H CH3 4--Cl--C6N~
S CIC~3313 CHICHI 2 H CH3 4--CH3--C6~4 6 CIC113 3 CHICH312 H CH3 4--OCH3--c6N4 20 7 C(CH3'3 CHICH312 H CH3 3,4--(OCH3~2--C6H3 8 CH(CH3)2 cyc70-C3H5 H CHI 4--cl-c6E~4 9 CH(CH3)2 Cyclo--C~H~ H CH3 4--Cl--C6N~
10 CN(CH3)2 Cyclo-C5H9 El CH3 4--Cl--C6Hq 25 1l CH(CH3)2 cyclr~C6HIl H CH3 4--Cl--C6 12 CH(cH3)2 CH2c6Hs H CH3 c6~s l3 CH(CH3 2 CH(CN3)C2El5 n CN3 C6H5 14 CH(CH312 Cll2cH(cH3)2 H CH3 C6H5 15 CH(CH3 2 CH(CH3)2 CH3 CN3 4--cl--C6U4 30 16 CH~cH3l2 Cl{~C6Hs H CH3 4--CH3--C6H4 17 CH(CH3 2 CN(CH3l2 H CH3 4--OCH3--CCH~
18 Cll(CH3,12 CH(CB312 H CH3 3~4-(ocH332-c6H3 19 C5Hs CH(CH3 2 H CH3 C6N5 35 20 C6H5 CH~CH31C2H5 H CH3 C6H5 21 C6H5 CH2CH(CH3)2 N CH3 C6N5 22 C6H5 CH(CH3)2 CH3 CH3 4--Cl--C6~
23 c6~s CH2C6Hs ~ CH3 4--CH3--C6H4 24 C6N5 CH(CH3)2 H CH3 4_oCH3--C6E~4 40 25 C6H5 CH(CH3)2 H CH3 3r4-(ocH3)2-c6H3 26 CHICH3l2 CH(CN3)2 H CH(CH3)2 cH2(4-cl-c6Eq) 27 CHICH3'2 CH(CH3)2 H CH(C83)2 Cli(CH3)(4--Cl--C6N4) 28 CH CH3 2 CH(CH3)2 71 CH(CH3)2 Cll(c6Hs)(4-cl-c6H4) 45 29 CHICT13)2 CH(CH3)2 H CN(CH3)2 4--Cl--C6H~
30 CH CH3)2 CN(CH3)2 CH3 CH(CH3)2 4--CH3--C6Hq 31 CHICH3)2 CH(CN3)2 H CH(CH312 4{7CH3--C6HI

0050~448g6 - 2 1 9 ~
.

Wo. R~ R3 R5 R6 R7 32 CH~CH31z CH(CN3)2 H CH(CH3)2 3,4--(OCH3)2--4E3 33 CH(CH31z CH(CH3)2 H CH2CH3 CH~(4--Cl--C6Hq) 34 CH(C8312 Cl~(CH3)2 H CH2CH3 CN cH3)(4-cl-c6H4) 35 CH(CH3 2 CH(CH3 2 H CH2CN3 CHlC6B5)(4--Cl--C6Hq) 36 CH(CH3 2 CHICH3 2 CH3 CN2CH3 4{83--c6H4 37 CH(CH3 2 CH~CH312 H CN2CH3 CH2(4--CR2--C6H5) 38 CH(CH312 CrrlCH3 2 H CH2CH3 4--oCH3--C6i~4 39 CH(CH3l2 CHICH3 2 N CH2CH3 3,4--(OCH3)ff6H3 40 CH(CH3 2 CHICH3 2 N Cyclo-C5H9 cH2(4-cl-c6H~) 41 CH(CN312 CH CH3)2 H cyclo-c5!~9 CH(CH3)(4--Cl--C6HI) 42 CH(CN3 2 CLI~CH3)2 H cyclo-CsBg CN(C6Hs)(4-cl-c6H4) 43 CH(CN312 CH(CH3)z H cyclo-csH9 4--Cl--C6H~
44 CH(CH3)2 CH(CH3)2 H cyclo-C5H9 4--CH3--C6H4 45 CH(CH3 2 CH CH3)2 H cyclo-csH9 4--OCN3_C6H;
46 CH(CH312 CiilCH3)2 H cyclo-csH9 3,4--(OCH3)2--C6H3 47 CN(CH312 CHICH3)2 H cyclo-C6Nl~ CH?(4-cl-c6H~) 48 CH(CH3~2 CH CH3)2 H Cyclo-c6Nll CH CH3~(4-cl-c6H4) 49 CH(CH3~2 CN CH3)2 H cyclo--C6Nll CH C6H5)(4--Cl--C6Hq~
CN(CH3~2 CNICH3~2 H cyclo-c6Hll 4{ L--C6H4 51 CN(CH3)2 CHICH3 2 H cyclo-c6Hll 4--CH3--C6H4 52 CH(CH3)2 CHICH3 2 H cyclo--C6H11 4--OCH3--C6H4 53 CH(CN312 CH CH3 2 H cyclo-C6H11 3,4--(0CH3)2--C6H3 54 CH(CH3 2 CillCH3 2 H CE3 4--C6H5--C6H-CH(CH3 2 CH CH31C2H5 N CH3 4--c6Hs-c6H4 56 CH~CH3 2 CH2CH(CH3)2 H CH3 4--C6Hs--C6H-57 CH(CH312 CH(CH3)2 N CH3 q--CF3--C6H4 58 CH(CH312 CH(CH3)2 H CH3 4--CW--C6H4 59 CN(CH3 2 CHICH3)2 H CH3 4--OC2HffcH4 CH(CH3 2 CHICH3)2 H CH3 4_OC6H5--C6H4 61 CH(CH3 2 CH CH3)2 H CH3 4--~--C6H4 62 CH(CH3~2 CHlcH3~2 H CH3 4--Br-C6H~
63 CN(CH3~2 CN CH3)2 H CH3 4--C(CH3~3--C6N4 64 CH(CH3~2 CH CH3~2 H CH3 Z--Cl--C6H4 CH(CH3~2 CHICH3~2 H CN3 3--Cl--C6H4 40 66 CH(CH3~2 CHICH3)2 H CH3 3~5-cl2-c6H3 67 CH(CH3~2 Cll CH3)2 H CN3 2,4--cl2--C6H3 68 CH(CH3)2 CH CH3~2 H CN3 2,6--C12--C6N3 69 CH(CH3~2 CH~CH3)2 H CH3 2--CN3--C6Hi CH(CH3)2 CH(CH3)2 H CH3 3--CN3--C6N4 45 7L CH(cH3)2 CH(CH3)2 H CH3 2,3--(CH3)2--4H3 7Z CH(CL13)2 CH(CH3)2 H CH3 2,4--(CH3)2--C6H3 ' 0050/44896 - 2 1 9 1 9 3 ~
.

No. Rl R3 R5 R6 R7 73 CHICH3 z cH(cu3 2 H CH3 3~s-(cH3l2-c6H3 74 CH CH3 2 CHICH312 H CH3 2,6-(CH3)2-C633 75 CHI C~J 2 CHICH3 2 H CHI 2-OCH3-C6H~
76 CNICH3 2 CHICH3 2 H CH3 3_oCH3-C6H~

78 CHICH3)2 CNICH3)2 H CH3 3-cc2Hs-c6H~
79 CH~CH3 2 CH(CH3)2 H CH3 2-OC2H5- 4 H1 10 80 CH(Ca3 2 CH~CH3)2 H CH3 3~4-(cc2Hs)2-c6H3 81 CH CH3 2 CH(CN3 2 H CH3 2-F-C6Hq 82 CHICH3 2 CH(CH3 2 H CN3 3-F-C6H4 83 CHICH3l2 CHICH3 2 H CH3 3-CH(CH3)2 84 CHICH312 CHICH3 2 H CN3 4-CH~CH3)~
85 CNlCH31z CHIC83 2 H CH3 2-CP3-C6H4 86 CHlcH3 2 C81CH312 H CH3 3-cF3-c6H4 87 CE(C83 2 CNICH3l~ CN3 CH3 C6H5 88 CH(CH3 2 CHICH31C2H5 CH3 CH3 C6H5 Z0 89 CH(CH3 2 CH2CN(CH3)2 CH3 CH3 C6Hs 90 CH(CH3 2 CH(CH3)2 CH3 CH3 4-Cl-C6H~
91 CH(CH3)2 CH(CH3)2 CH3 CH3 4-CH3-C6H4 92 CH~CH3)2 CHiCH3)2 CH3 CH3 4-OCH3-C6N4 93 CH(CH3)2 CH~CH3)2 CH3 CH3 3 4-(CCH3)2-C6H3 25 94 CN(CH3)c2Ys CN CH3)2 H CH3 4-Cl~C6Hq 9S CH CH3)C2H5 CHlcH3)c2H5 H CH3 4-cl-C6H4 96 CHICH3)C2H5 CH;CH(CH3)2 H CH3 4-Cl-C6H~
97 CH(CH3)C2H5 CH CH3~2 CH3 CH3 4-CH3-C6H~
30 98 CHICH3)C2H5 CHICH3 2 H CH3 4_oCH3-C6H4 99 CHICH3 C2H5 CHICH312 H CH3 3 4-(OCH3)2-C6N3 100 CH(CH31C2n5 CHICH3 2 H CH3 cH2(4-cl-c6H4) 101 CH(CH31C2H5 CHICH312 H CH3 CH(C6H5)(4-Cl-C6H4) 102 CH~CH3 C2H5 CH CH3 C2H5 H CH3 4-Cl-C6H4 103 CH2-C6E5 CH;CH(CH3)2 H CH3 4-cl-C6H4 104 CE2-C6H5 CHICH3J2 CH3 CH3 4-Cl-C6H4 lOS CH2-(4-CH30-C6H~) CHICH3 2 H CH3 4-Cl-C6H~
106 CH2-(4-cH3-c6H~) CHICH312 H CH3 4-Cl-C6H~
~o 107 CH2-(4-cl-c6H~) CH CH312 H CH3 4-Cl-C6Hq L08 4-Cl-C6H~ CHICH3 2 H CHJ 4~Cl-C6Hq 109 4-CH3-C6H4 C3 CH312 H CH3 4-Cl-C6Hq 110 4-CH30-C6a4 CH CH3 2 H CH3 4-Cl-C6H~
111 4-C6F5-C6Bq C31CH3 2 H CH3 4-Cl-C~H~
112 Cyclo-csH9 CH CH3)2 H CH3 4-Cl-C5Hq 113 cyclo-c6Hll CH CH3)2 H CH3 4-Cl-C6H~

_ ~

~ 25 2~g~ g39 No. Rl R3 R5 RC R7 114 C~Hs CH'CH3 z H CH3 4--CI--C6H4 115 CHzCH2CH3 CH CN3 2 H CH3 4--CI--C6H4 116 CH~CH2CH2CH3 CH1CH3'2 H CH3 4--CI--C6H~
117 CHlCH(CH3)2 CY CN3 i Y CH3 9--CI--C6H4 118 (CHz)~CH3 CHICH3 ~ H CN3 4--cI--C6H4 117 (cH2)scH3 CY1CN3 2 H CH3 4--CI--C6H
120 ClCH2CHz CHICH3)i H CH3 4--Cl--C6H~
121 C13CCH2 CH CH3)2 H CN3 4--Cl--C6H~
122 CH30CH2CH2 CHICH3)2 H CH3 4--CI--C6H4 lZ3 CHz-CH CH1CH3 2 H CN3 4--CI--C6Hq I24 CH30CH2CEi~CH3) CB CR3 2 H CH3 4--CI--C6H~
125 Cl(CH3)CH CH CE13 2 H CH3 4--CI--C6H~
126 C6RsocH2cH2 CHlcH3~2 H CH3 4--Cl--C6H, 127 CH2=C(CH3) CH1CH3 2 H CH3 4--C1--C6H~
128 CH(CH3)2 CEi~CY3 2 H C6Ei5 cH2(4-cl-c6H4) 129 CH(cH3)2 CH(CH312 H C6H5 CH(CH3)(4--CI--C6H~) 130 CH~CH3)2 CH(CH3 2 N C6H5 cN(c6H5)(4-cl-c6H4) 131 CH(CH3)2 CH(CH3 2 H C6H5 4--Cl--C6H4 132 cHtca3)2 C8(CE13)2 H C6H5 4--CH3--C6H4 133 CH CH3)2 CH(CH3)2 H C6H5 4--oCH3--C6H4 134 CH~CH3)2 cycIo--C3H5 H C6H5 4--Cl--C6H4 135 CH~ CH3)2 cyclo-c~H7 H C6H5 4_cl--C6H4 136 CNI CH3~2 cycI~C5H9 H C6Hs 4--CI--C6Ei~
137 CHICH312 cycIo-C6Hl~ H C6Hs 4--CI--C6E!4 138 CHICH3 C2H5 CH(cN3)2 H CH1CH3)2 4--CI--C6H~
139 CH~CH3 C2H5 CH(CHl)C2Hs H CH~CEi3)2 4--CI--C6H-lgO CHICH3 C2Hs CH2cH(cH3)2 li CH CH3)2 4--Cl--C6H4 141 CH(CH31C2Hs CH(CEil)2 H CHICH3)2 4--Cl--C6H4 142 CH1'CH3 C2Hs CHICH3)2 El CH1CH3)2 4--cl-c6H4 143 CH CH31C2Hs CHICE}3)2 H CH CH3)2 4--CI--C6H, 144 CN CH3 C2H5 CHICE13)2 H CH1CH3)2 4--CI--C6H4 145 CHICH31c2Ns CH(CH3)2 H CHICN3)2 4--CI--C6H~
146 CHICH3 C2Hs CH(cH3)c2Hs H CHICH3)2 4-cl-c6H~

I4 7 C H2--C6E5 CH2CH(CH3)2 H CB CH3)2 4--C 1--C6H~
148 CH~--C6H~ CH(CH3)2 H CH(CH3)2 4--CI--C6Hq 149 CH2--l 4--CH3O--C6Eil) CH(CH3)2 H CH(CH3)2 4--CI--C6H4 150 CH2--14--CH3--C6HG) CH(CH312 H CH(CH3)2 4--CI--C6H4 151 CH2--14--Cl--C6HG) CH(CH312 H CH CH3)2 4--Cl--C6H4 152 4--Cl--C6H~ CH(CFi3~2 H CH CH3)2 4--C1--C6H~
4'i 153 4--CH3--C6H4 CH(CH3)2 H CH CH3)2 4--Cl--C6H4 154 4--CH3O--C6HG CH(CEi3)2 H CH CH3)2 4--Cl--C6H~

. _ _ _ _ _ _ . .. . . . . : . . . . _ . _ .

0050~44896 2 1 9 ~ 9 9 9 ~o. R1 R3 R5 R6 R7 lSS 4-C6Hs-C6H~ CH~CH3)2 H CN CH3I~ 4-Cl-C6H4 156 cyclo-C5Hg CHICH3)2 H CHICH3 2 4-Cl-C6H~
LS7 cyclo-C6NIl CHICH3)2 H CHIC~3l2 4-Cl-C6H~
158 C2Hs CHICH3)2 H CHICH3 2 4-Cl-C6H6 lS9 CH2CHzCH3 CHICH3 2 H CNICH3 2 4-Cl-C6H~
160 CH1CH~CH2CHI CH~CH3 2 H CHICH3)2 4-cl-c6H~
161 CH2cH(cH3)2 CH(CH3 2 H CH CH3)2 4-Cl-C6H~
10 162 (CN2)~CH3 CH(cH3 2 H CHIcH3 2 4-Cl-C6H~
163 (CH2)sCH3 CHICH3 2 H CH CH312 4-Cl-C6H~
164 ClCH2CH2 CHICH3 2 H CHICH3 2 4-Cl-C6H~
165 C13CCN2 CHICH3 2 H CHICa3 2 4-Cl-C6N~
166 CH3OC~2Ca2 CHICH3 2 N CH CH3I2 4-Cl-C6H4 15 167 CH2=C~ CHICH3 2 H CH~cH3l2 4-Cl-C6H~
168 C~3OC~2C~(CH3) CHICH3 2 N CaICH3l2 4-Cl-C6H~
169 Cl(CH3)CH CHICH3 2 H CBICE3I2 4-Cl-C6H~
170 C6HsOCH2CH2 CHICa3)2 N Ca~Cà3 2 4-cl-c6a~
20 171 CH2=c(cH3) CH CH3)i H CH CH3)2 4-C1-C6H~
172 C6Hs CH CH3)2 H cyclo-C3H5 C6H5 173 C6H5 CHICH3)2 H cyclo-C3Hs 4-cl-c6a~
174 C6Hs CHlCH3 2 ~ cyclo-C3Ns 4-CH3-C6H4 175 C6Hs CH(CH3 2 H cyclo-C3Hs 4-OCH3-C6H~
176 C6Hs ca CH3 2 H cyclo-c3Hs 3 4-(oc03)2-c6H3 172 CH(CH3)2 CH CH3~2 H cyclo-C3H5 C6H5 173 CH(CH3)~ CHICH3)~ H cyclo-C3H5 4-cl-c6a~
174 CH(CH3)2 CHICH3)2 a cyclo-C3H5 4-CH3-C6 175 CH(CH3)2 CHICH3)2 H cyclo-C3~s 4-CCH3-C6H~
176 ca(cH3)2 CHICH3)2 ~ cyclo-C3as 3,4-(ocH3)2-c6H3 177 CH(CH3)2 CH~CH3)2 a CE2CH(CH312 4-Cl-C6H~
178 CH~CH3)2 CH(CH3)2 N CH3cH2cH2 4-CH3-C6H-179 CHICH3)~ CH(CH3 2 N CH3(CX2)3 4-Cl-C6H-180 cnlcH3)2 CH(CH3 2 H CH~CH2CH3)2 4-CH3-C6H-181 ClCH3)3 CH~CH3I2 H CH3 C6Hs 182 CH~CH3)z CH~Cal 2 B CH3 C6H5 163 C6H5 CH6CH3~2 H CH3 C6H5 184 CH~CH3)2 CH CH3)2 H CH3 4-CH3-C
189 C6H5 CH CH3)2 H CH3 4-CH ff 6a~
186 CN(Cn3)C2Hs CHlCH3)2 N CH3 4-CH3-C6N~
186 cn2cH(cH3)2 CHICH3)2 H CH3 4_CH3-C6H-188 CH2C6H5 CHIC~3)2 H CH3 4-CH3-C6n-189 CH(CH3)2 CH(CH3)2 H CH3 4-Cl-C
190 C6H5 CH~CH3)2 H CH3 4-Cl-C

0050/4~896 27 ~ 2 1 9 1 9 9 N~. Rl R3 R5 R6 ~7 191 CH2C6Hs CH~C~3~2 H C~3 4-Cl-C5Hq l9Z C(CH1~3 C~(C~3)2 ~ C2H~ 4-CH3-C6 193 CH(CH3~1 C~(C~312 ~ C2H5 4-CH3-C6 194 CB(CH3lC2Hs CH~C~3 2 H C2Hs 4-CH3-C6H~
195 C(CH3~3 CN(CH3 2 H C2Hs 4-cl-C6H4 l9G CH(CH3~2 CH CH312 H C2Hs 4-Cl-CGHq 197 CH(C~3~C~Hs CHlcH3 12 H C2Hs 4-Cl-C6H~
10 198 CH(CH3~2 cH~aHl~2 ~ CN(C~J~2 4-CH3-C6H
199 CH(CH3~ClHS CHICH3 2 H C8(C~3)2 4-CH3-C6H~
200 C(CH3~3 CH(CH3~2 ~ H 4-Cl-C6H~
201 C(CH3~3 c~(cN3 2 H H 4-CR3-C6H
15 202 C(CH3)3 CH~CH312 H CH(CH2CH3)2 4-CH3-C6H4 203 C(CH3)3 CH(CH312 ~ (CH2)3cH3 4-CH3-C6H~
204 C(CH3)3 CH(CHI)2 ~ cyclo-C5H9 4-CH3-C6H~
205 C(CH3)3 CH(CH3~z ~ (C~l)3Cl73 4-cl-C6R4 286 C(cH3)3 CH(CH3)2 ~ cyclo-C5H9 4-Cl-C6H~
20~ C(CB3)2 CH(CH3)2 H n-CsHll 4-CH3-C6H~
208 C~CH3)2 CH(CH3)2 ~ n-C6HIl 4-CH3-C6B4 209 C C~3)2 CH~CH3)2 H n-C7Nl5 4-CH3-C6Hq 210 C~cH3)2 CH~CH3)2 8 n-ct~l7 4-CH3-C6H~
z9 211 C(C~3)2 CH CH3~2 H CH2-C(CH313 4-c~3-c6H4 212 C(CH3)2 CH~CH3)2 H C(CH312C2Hs 4-CHI-C6Hq 213 C(CH3~2 CH(CH3)2 H CH(CH3lC3H7 4-CH3-C6H4 214 C(CH3)2 CH~CH3 2 ~ n-C5~ll 4-cl-c6H4 30 215 C(CH3)2 CB(CH3 2 H n-C6H11 4-Cl-C6H~
216 C(CH3)2 CHICH3 2 ~ n-C7NIs 4-Cl-C6H~
217 C(CH3)2 CH~CH3 2 H n-CaH,7 4-Cl-C6H
218 C(CH3)2 CBlCH3)2 H CH2-C(CH3~3 4-Cl-C6H4 219 C(CH3)2 CHIC~3)2 H c(cH3~2c2Ns q-cl-c6H~
220 C(C~3)2 CH~CH3)2 ~ CH~cH3)c3H7 4-Cl-C6H4 0050~4489~
21 ~199~

~a~le 3 0 H R3 ~ R5 R5 Rl_xl--C--N--C --C--~-- N--X{~

Xl is oxygen or sul~ur.
No. R~ R3 Rs R~ X Z
C(CE~3)3 CH(CH3)2 H CH3 -- 4--Cl 15 2 C(CH3)3 CH(CH3)2 n C~3 -- 4--CE~3 3 C(C1~3 13 CH(CH3)2 H CH3 4--OCE13 4 c(cHl)l CH(CK3 2 H CH3 8 4--(OCH3)2 CHICH3 2 CH(CH3l2 H C~3 -- H
20 6 CHiCH3l2 CH(CH3l2 H CH3 -- 4--Cl 2 CH~CH3 2 CH(CH3)2 H CH3 -- 4--CH3 8 CHiCH3l2 CH(CH3)2 H CH3 -- 4--OCH3 g CH~CH3 12 CH(CH3)2 H CH3 -- 3,4--(OCH3) C6H5 CH(CH3)2 H CH3 -- H
11 C6H5 CHlcH3)2 H CH3 -- 4--C1 I2 C6H5 CH~CH3)2 H CH3 -- 4--CH3 13 C6H5 CH,CH3)2 H CH3 -- 4--OCH3 14 C6H5 CHICH3)2 H CH3 -- 3 4--(OCH3)2 30 15 CH(cH3)2 CHICH3)2 H CH(CH3)2 CH2 4--Cl 16 CH(CH3)2 CHI~CH3 2 H CH(CH3)2 -- 4--Cl 17 CH(CH3)2 CH~CH3l2 H CH2CH1 CHCH3 4--CL
18 CH(C~3)2 CHICH3l2 H CH2CH3 CHC6H5 4--Cl 35 19 CHICH3)2 CHICH3 2 H CH2CH3 ~ 4_Cl cnrCH3) 2 CHICH3)2 H cyclo-c5H9 -- 4_Cl 21 CH CH3)2 CH~CH3)2 N cyclo--C6H11 -- 4--Cl 22 CHiCH3)2 CHIC83)2 H CE~3 -- 4--CH(CH3)2 CH(CH3)2 CH~CH3)2 CH3 CH3 -- 4--Cl 24 CH(CE13)2 CHICH3)2 CH3 CE~3 -- 4_CH3 CH(C113)2 CHICH3)2 CH3 CH3 -- 4--OCH3 26 CH(CH3)2 CH~CH3)2 CH3 CH3 -- 3,4--(OCH3)2 27 CH2C6Hs CHICH3)2 H CH3 -- 4--Cl 2B cyclo--C6Hll CHICH3~2 1; C~3 -- q--Cl 29 CH2C~(CH3)2 CHICH3~2 H CH3 -- 4--Cl ' 0050r44896 2 1 ~ 1 ~ 9 ~
.

No. Rl R3 Rs R6 X Z
30 CH(CH332 CHICH3J2 H C6H5 - 4-Cl 31 CH(CH31~ CHICH3)2 H C6Hs - 4-CH3 5 32 CH(CH3)2 CH~CHI)2 H C6Hs - 4-OCH3 Table 4 Wl\ O H ~3 ~ Rs R6 C=N--O--C - N - C - C - N - N - R7 w2 Ls No. W1 W2 R3 Rs R6 R7 1 CH3 CH3 CH(cH3)2 H CH3 OCH3-C6H~
2 CH3 CH3 CH~CH3 2 H CH3 3,4-(OCH3)2-C6H3 20 3 CH3 C6H5 CH(CH3 2 H CH3 C6H5 4 CH3 C6H5 CH(CH3 12 H CH3 4-Cl-C6H4 CH3 C6H5 CH(Cc3 2 H CH3 4-CH3-C6H4 6 C~3 C6H5 CH(cH3 2 ~ CH3 4_ocH3-c6Hç
25 7 CH3 C6R5 CH(CH3 '2 H CH3 3,4-(OCH3)2-C6H3 ~3 CH3 4-CH3-C6H4 CH(CH3~2 H CH3 C6Hs 9 CH3 4-CH3-C6H4 cn(cH3l2 H CH3 4-Cl-C6H4 CH3 4-CB3-C6H4 CH(CH3~2 H CH3 4-CH3-C6H4 30 11 CH3 4-CH3-C6H4 CH(CH3 2 H CH3 4_ocH3-C6H4 12 CH3 4-CH3-C6H4 C~(CH3 2 H CH3 3,4-(OCH3)2-C6H3 13 CH3 4-CH3-C6H4 CH(CE3 2 H CH(CH3)2 CH2(4-Cl-Cc 14 CR3 4-CH3-C6H4 CH(CH3 2 H CH(CH3)2 4 - Cl - C6H4 lS CH3 4-CH3-C6H6 CH(CH3 12 H CH2CH3 CH(CH3)(4-Cl-C6H6) 16 CH3 4-CH3-C6H4 CH(CH3 2 H CH2CH3 CH(c6Hsl(4 17 CH3 4-Cl-C6H4 CH(CH3 '2 H CH3 C6H5 18 CH3 4-cl-C5H4 CH(CH3 2 H CHl 4-C1-C6H~
19 CH3 4-Cl-C6H4 CH(CH3)2 U C~3 4-CH3-C6H4 4~ 20 CH3 4-Cl-C6H~ CH(CH312 H CH3 4_OCH3-C6H4 21 CH3 4-Cl-C6H4 CH(CH3)2 H CH3 3,4-(0CH3)2-C6H3 22 CH3 4-C1-C6H4 CH(CH3)2 H CH(CH3)2 CH2(4-Cl-4 H4) 23 CH3 4-Cl-C6H4 CH(CH3)2 H CH(CH3)2 4-C1-C6H4 45 24 CH3 4-Cl-C6H4 CH(CH112 H CH2CH3 cH(cH3l(4-cl-c6~4l CH3 4-Cl-C6H~ CH(CH312 H CH2CH3 CE(C6Hs)(4-Cl-C6H4) 0050~44~96 ~ 30 No. W~ w2 R3 Rs R6 R7 26 CH3 CH3 CH~CH3)2 H CH3 4-Cl-C6H4 27 CH3 CH3 CH(CH312 H CH3 4-CH3-C6H~

~able 5 S H (cH3)2cH o H R5 Rl----S--C--N--C--C--N--N ~ R3 No. Rl R5 R8 l CH(CH3)2 c~3 CH3 2 CH(CH3) 2 CH3 Cl 8 CH(CH3)C2~s CH3 CH3 20 4 CH(CH3)C2~s c~3 Cl 6 CH2C6H5 CH3 Cl 7 C~C~3)2 C2~5 c~3 25 8 CH~CH3)2 C2H5 Cl g CHICH3)2 CH(CH3)2 CB3 CHICH3)2 CH(CH3)2 Cl 11 CH~cH3)2 n-4Hg c~3 30 12 CH(C83)2 CH2CH(CH3)2 Cl 13 CH(CH3 2 n-C~Hg CH3 14 CH(CH3~2 CH2CH(CH3)z Cl CH(CH3.'2 CH(Cz~s)2 CH3 16 CH(CH3)2 CH(C2Hs)2 Cl 35 17 CH(CH3)2 CH2-CsHS CH3 18 CH(CH3) 2 CHZ-c6Hs Cl l9 c(CH3)3 Cyclo-C5Hg CH3 CH(CH3)2 cyclo-C5H9 CH3 40 21 CH(CH3)C2H5 cyclo-C5H9 CH3 22 C(CH3)3 cyclo-C5Hg Cl 23 CH(cH3)2 cyclo-C5Hg C1 2G CH(CH3)C2Hs cyclo-C5Hg Cl C(C~3)3 cyclo-C6Hl1 CH3 26 CH(CH3)2 cyclo-C6Hll CH3 27 c~(cH3)c2Hs cyclO-c6Hll CH3 . 0050/4~896 ' 2 1 5 ~

No. Rl R6 R8 28 C~CH3)3 cyclo-c6Hll Cl 29 CH(CHJ)2 cyclo-c6Hll Cl 5 30 CH(CHl~QH5 cyclo-C6Hll Cl 31 CH(CH3 2 C6Hs CH3 32 CH(CH3l2 CH(CH3)C2HS Cl 33 CH~CH3)2 C6H5 CH3 34 CH(CH3)2 CH(CH3)C2HS Cl Table 6 S H (CH3)2CH o H R6 R~O--C ~ C --C_ 17 _ N ~=~ R
H

No Rl R5 RB
CH(CH3)2 CH3 CH3 2 CH(CH3 12 CH3 Cl 25 3 CH(CH3 C2H5 CH3 CH3 4 CH(cHl)c2~s CH3 Cl CH2C6Hs CH3 CH3 6 CH,C6Hs CH3 Cl 3o 8 CH CH3 2 CzHs Cl g CHICH3l2 CH CH3)2 CH3 CH(CH3 2 CHICHJ)2 Cl 11 CHICH3 2 n-C4Hg CH3 3S 12 CH(CB3 2 n-C4Hg Cl 13 CH~CH3)2 CH2CH~CH3)2 CH3 14 CH(CH3)2 CH2CH~CH312 Cl CH(CH3)2 CH(C2~s)2 CH3 40 16 CHICH3l2 CH(C2Hs)2 Cl 17 CHICH3~2 CH2-C6H5 CH3 18 CH~CH3~2 CH2-C6H5 Cl 19 C~CH3)3 cyclo-csH? CH3 CH~CH3)2 cyclo-C5Hg CH3 21 CH~CH3)C2~s CyClO-CgHg CH3 22 C(CH3)3 cyclo-c5H? Cl 0050/44896 2 1 9 1 9 ~ ~
.

No. Rl R6 ~3 23 CH(CH3)2 cyclo-CsHg Cl 24 CH(CH3)CzHs cyalo-Csag Cl 5 25 C(CH3)3 CyclC-c6Hll CH3 26 C~ICH3)2 cyclo-c6Hll CH3 27 CH~C~3)C2H5 cyclo-c6HLl CH3 28 C(CH3)3 cyclo-c6Hll C1 29 CHlCH3)2 cyclo-C6Hll C1 CH~CH3~C2Hs CyclO-C6HIl C1 31 CH CH3)2 C6HS CH3 32 CHICH3)2 C6H5 Cl 33 CH(CH3)2 CH(cH3)c2Hs CH3 15 34 CH(CH3)2 CH(CH3)C2~5 Cl The novel ~iullds of the formula I are suitable as fungicides.

The novel ~ ~ , or the compositions containing them, can be 20 applied for example by bpraying, atomizing, dusting, scattering or watering in the form of directly sprayable solutions, powders, suspensions, even high-percentage aqueous, oily or other suspen-sions or dispersions, lci~n~, oil dispersions, pastes, dusting compositions, scattering compositions or granules. ~he applica-25 tion forms depend on the intended uses; in each case they shouldif possible ensure the finest dispersion of the active compounds according to the invention.
~ormally, the plants are sprayed or dusted with the active com-30 pounds or the seeds of the plants are treated with the active Ulllg .

The formulations are prepared in a Icnown manner, eg. by extending the active compound with solvents and/or carriers, if desired 3!i using : l~;f;~r5 and dispersants, where if water is used as a diluent other oryanic solvents can also be used as auxiliary sol-vents. Suitable auxiliaries for this purpose are mainly: solvents such as aromatics (eg. xylene), chlorinated aromatics (eg chlolobD~ " ,), paraffins (eg. petroleum fractions), alcohols 40 (eg. methanol, butanol), Icetones (eg. cycl~h~n~n~), amines (eg~
e~h~n~l~min~, dimethylformamide) and water; carriers such as ground natural minerals (eg. kaolins, aluminas, talc, chalk) and ground synthetic minerals (eg. highly disperse silica, silicates), l5ifi~rs such as nonionic and anionio emulsifiers g5 (eg. polyoxyethylene fatty alcohol ethers, allcanesulfonates and .. . _ . . . . . . _ _ _ _ . _ _ _ _ _ . . . .

0050/44896 ~ 9 9 ~

~ 33 arylsulfonates) and dispersant9 6uch as lignin-sulfite waste liquors and methylce~ lose.

suitable surface-active substances are the alkali metal, alkaline 5 earth metal and ammonium salts of aromatic sulfonic acids, eg.
l;gn~ 1fonic, rhorol~ fo~i~, naphthalenesulfonic and dibutyl-naphthalenesulfonic acid, and also of fatty acids, alkyl- and alkylarylsnlf~n~ , alkyl-, lauryl ether and fatty alcohol sulfates, as well as salts of sulfated hexa-, hepta- and octa-1~ decanols, and also of fatty alcohol glycol ethers, condensationproducts of sulfonated naphthalene and its derivativeg with formaldehyde, condensation products of naphthalene or of the naphthalenesulfonic acids with phenol and formaldehyde, polyoxy-ethylene octylphenol ether, ethoxylated isooctyl-, octyl- or 15 nonylphenol, allcylphenol- or tributylphenylpolyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide ~ delsates, ethoxylated castor oil, polyoxyethy-lene alkyl ethers or polyu~y~Lu~ylene tsicj, lauryl alcohol polyglycol ether acetate, sorbitol esters, lignin-sulfite waste 20 liquors or methylcellulose.

Powder, scattering and dusting compositions can be prepared by mixing or joint grinding of the active substances with a solid carrier.
Granules, eg. coated, impregnated and h~ , granules, can be prepared by binding the active ~ _ ' to solid carriers Solid carriers are mineral earths such as silica gel, silicic acids, silica gels [sic~, silicates, talc, kaolin, limestone, 30 lime, chalk, bole, loess, clay, dolomite, dial ~L earth, calcium sulfate and magnesium sulfate, m-gn~ m oxide, ground synthetic materials, fertilizers, such as ammcnium sulfate, ammo-nium i?h~sphlte, ammonium nitrate, ureas and vegetable products, such ~ cereal flour, tree bark meal, wood meal and nutshell 35 meal, co~ lo8e powder or other solid carriers.

Examples of such preparations are:

I. a solution of 90 parts by weight of a compound I accord-ing to the invention and 10 parts by weight of N-methyl-2-pyrrolidone, which is suitable for application in the form of very small drops II. a mixture of 10 parts by weight of a compound I according to the invention, 70 parts by weight of xylene, 10 parts by weight of the addition product of from 8 to 10 mol of ethylene oxide to 1 mol of oleic acid ~-monoe~h~nolam~

_ _ _ , , , . . , ... , . , . _ . , _ ,,, , . _, , 005~/44896 2 1 9 ~ 9 9 9 ~ 34 5 parts by weigh~ of calcium salt of dodecylbenzene-sulfonic acid, 5 parts by weight of the addition product of q0 mol of ethy~lene oxide to l mol of castor oil, a dispersion is obtained by finely dispersing the solution s in water.

III. an aqueous dispersion of l0 parts by weight of a oompound I according to the invention, 40 parts by weight of cyc1nh-Y~,--..r, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 40 mol of ethylene oxide to l mol of castor oil IV. an aqueous dispersion of l0 parts by weight o~ a compound I according to the invention, 25 parts by weight of cyr3~h~nnl, 55 parts by weight of a petroleum fraction of boiling point from 210 to 280'C, and l0 parts by weight of the addition product of 40 mol of ethylene oxide to l mol of castor oil;

20 V. a mixture, ground in a hammer mill, of 80 parts by weight, preferably of a solid compound I according to the invention, 3 parts by weight of the sodium salt of diiso~
butylnaphthalene-2-6-~1fonic acid, l0 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 7 parts by weight of powdered silica gel; a spray liquor is obtained by finely dispersing the mixture in water;

VI. an intimate mixture of 3 parts by weight of a compound I
according to the invention and 97 parts by weight of finely divided kaolin; this dusting . i~;nn contains 3i by weight of active compound;

VII. an intimate mixture of 30 parts by weight of a compound I
according to the invention, 62 parts by weight of powdered silica gel and 8 parts by weight of liquid paraffin which has been sprayed ODto the surface of this silica gel; this preparation gives the active compound good adhesion;
gO
VIII. a stable aqueous dispersion of 40 parts by weight of a compound I according to the invention, l0 parts by weight of the sodium salt of a phenolc--1fon;c acid/urea/formal-dehyde condensate, 2 parts by weight of silica gel and 48 parts by weight o~ water, which can be further diluted;

_ _ _ _ _ . _ _ _ _ . .

~ - 2 ~
' OOSO/44896 .

IX. a stable oily dispersion of 20 parts by weight of a com-pound I ~cnr~ing to the invention, 2 parts by weight of the calcium salt of dodecylh~ n-~ lfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by S weight of the sodium salt of a rh~nnlc~llfoni~ acid/urea/
fnr~ hyde condensate and S0 parts by weight of a paraffinic mineral oil.
The novel , ~c are distinguished by an outstanding activity 10 against a broad spectrum of phytopathogenic fungi, in particular from the class of D~hLel~ e3, As~ I eLe~, ~hi~ ~ ~Les and Bas;~;~ y~_Les. They are systemically active in some cases and can be employed as foliar and soil fnngir;~c l'i They are of particular - ~ ~a~ for the contrcl of a multi-plicity of fungi on various crop plants such as wheat, rye, barley, oats, rice, corn, lawns [sic], cotton, soybeans, co~fee, sugar cane, grapes, fruit and decorative plants and vegetable plants such as ~u- a, beans and cucurbits, and on the seeds Z0 of these plants.

~he , ' are applied by treating the fungi or the seeds, plants, materials or the soil to be ~l~-e~-ed from fungal attack with a fungicidally effective amount of the active c ~c.
2ri They are applied before or after the infection of the materials, plants or seeds by the fungi.

The novel c ~ n~C are specifically suitable for the control of 30 the following plant diseases:

Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on cucurbits, po~n5rh~ra leucotricha on apples, uncinula necator on vines, 35 Puccinia ~pecies on cereals, Rhizoctcnia species cn cotton and lawns lsic], Ustilago species on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helminthosporium species on cereals, Septoria nodorum on wheat, Botrytis cinerea ~gray mcld) on straw-berries, vines, decorative plants and vegetables, C~1~0~L~
40 ara~hi~i~nl~ on groundnuts, Pseudo~ y~,~lla herpo~ri~hni~ec on wheat, barley, Pyricularia oryzae on rice, ~hytcphthora infestans on potatoes and tomatoes, Eusarium and ver~ -m species on various plants, ~lasmopara viticola on vines, ~ rn~r;~ species on vegetables and fruit.

' 0050/~4896 2 ~ 9 ~
.

~ 6 The novel ~ ' can also be employed in the proteation o~
materials ~UL.3aIvation of wood), eg. against PRe~ 5 variotii.

5 The iungicidal compositions in general contain from ~.1 to 95, preferably from C.5 to 90, % by weight of active compound.

Depending on the type of effect desired, the application rates are from 0.025 to 2, preferably from 0.1 to 1, kg of active com-10 pound per ha.

In seed treatment, amounts of active compound of from 0.001 to50 g, preferably 0.01 to 10 g, per kilogram of seed are in gener~l needed.

The compositions according to the invention can also be present as fungicides together with other active ~ '- in the application form, eg. with h~rhic;~, insecticides, growth regu-lators, fungicides or alternatively with fertilizers.
Cn mixing with f~lng;~ s, in many cases an increase in the fun-gicidal spectrum of action is obtained here.

The following list of f-~n5;~ with which the ~ ~ -Z5 according to the invention can be applied together is intended to illustrate the combination possibilities, but not restrict them:

sulfur, dithiocArh-~t~c and their derivatives, such as ferric dimethyldi~hionR-- ~, zinc dimethylrlilhi~ - Le, zinc 30 ethyl~n~h;~;thiocarbamate, manganese ethyl~r~hic~;thiocRrh~-te, manganese zinc ethyl~n~liRm;nr~ bisdilhinnR-' ~e, tetramethyl-thiuram disulfide, ammonia complex of zinc N,N-ethyl~n~hi~ithi c~ e, ammonia complex of zinc N~N~-propylenebisdilh;ocRrha mate, zinc N,N'-propyl~n~hi~ hinc~--'- Le, N,N~-polypropylene-35 bis(thiocarbamoyl) disulfide;

nitro derivatives, such as dinitro~l-methylheptyl)phenyl croto-nate, 2-sec-butyl-4,6-dini~rophenyl-3,3-dimethylacrylate, 2-~ec-butyl-4,6-dinitrophenyl isopropyl carbonate, diisopropyl 40 5-nitroisophthalate;

heterocyclic subs~ances, such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6-~o-chloroanilino)-s-triazine, 0,C-diethyl phShAl;mi~nphn~rhnnothioate, S-amino-l-[bis~dimethylamino)-phos-g5 phinyl]-3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-di~h;nAnthra-quinone, 2-thio-l~3-dithiolo[4rs-bl~ll;nn~Al;n~r methyl l-~butyl-carbamoyl)-2--b~n?;m;~lA?Ol~n~ 2-methv.. ,~ L~,n~lamino-0050~g48~6 ~ 1 9 1 9 3 3 bDn7i~;~7nl~, Z-(fur-2-yl)b~n7imi~701e, 2-[thiazolyl-4-yl)b~n7im;~A7Qle, N-(1,1,2,2-tetrachloroethyl-thio)tetrahydrophthRlimi~D~ N-trichlor~ethylthiotetra-hydroph~halimi~D, N-trichloromethylthiophthRli~i~P, N-dichlorofluoromethylthio-N~N~-dimethyl-N-phenyl ~nl f~ r~
5 cthoxy-3-trichloromethyl-1,2,3-~hi--~iR7nl~, 2-thiocyanato-methyl~hioh~n7othiazole~ 1,q--dichloro-2,5-dimethoxybenzene, 4-(2-chloropheny~lhydrazono)-3-methyl~5-icnvR7ol~ --, 2-thiopyri-10 dine-1-oxide, 8-LydLu~y~uinoline or its copper salt, 2,3-dihydro-5-carboY~nili~n-6-methyl-l~4-oxathiin~
2,3-dihydro-5-rRrhov~nili~n-6-methyl-1,4-oxathiin-4,4-dicxide, 2-methyl-5,6-dihydro-4H-pyran-3-carhnYRnilide~ 2-methyl-f uran--3--c arbnY R ni 1 i rl~ ~ 2,5-dimethylfuran-3_~rhnYRnili,~, 15 2~4~5-trimethylfuran-3-carhnyRnilir~ N-cyclohexyl-2,5-dimethyl-furnn-3-ca.b ~1D, N-cyclohexyl-X-methoxy-2,5-dimethyl-furan-3-ca~' d~, 2-methylhDn7Rnil;,lD, 2-in~ r~, U-formyl ll ~holine-2,Z,2-trichloroethyl acetal, pipera-zine-1,4-diylbis(1-(2,2,2-trichloroethyl))formamide, 20 1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane, 2,6-dimeLhyl-N-tridecylmorpholine or it5 saLts, 2,6-dimethyl-N-cyclododecylmorpholine or its salts, N-[3-(p-tert-butyl-phenyl)-2-methylpropyll-cis-2,6-dimethylmorpholine, N-[3-(p-LelL ~uLylphenyl)-2-methylpropyll-piperidiner 25 1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-yl-ethyll-l~-1,2,4-tria_ole, 1-t2-(2,4-dichloro-phenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-lh-1,2,4-triazole, N-(n-propyl)-N-~2,4,6-trichluLu~L_..u~y~Lhyl)-N'-imidazolylurea, 1-(4-ohlvLupl,eno~y)-3,3-dimethyl-1-(1~-1,2,4-tria-30 zol-1-yl)-2-butanone, (2-chlorophenyl)-(4-chlorophenyl)-5-pyrimi-dinemethanol tsic]r S-butyl-2-dimethyl_mino-4-hydroxy-6-methylpy-rimidine, bis(p-chlorophenyl)-3-pyridinemethanol, 1,2-bis(3-eth~y~.bu..yl-2-thioureido)benzene, 1,2-bis(3 . Lho~y~lbvl,yl-2-thioureido)benzene, t2-(4-chlorophenyl)ethyl]-(1,1-dimethyl-35 ethyl)-1~-1,2,4-triazole-1-ethanol ~sicl, 1-t3-(2-chlorophenyl)-1-(4-fluu~u~ nyl)oxiran-2-ylmethyll-lH-1,2,4-triazole, and various fungicides, such as dodecylguanidine acetate, 3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-1.yd.u~y~Ll.yllglutarimide, ~o hDY~hlnrobenzene, DL-methyl-N-(2~6-dimethylphenyl)-N-2-furoyl alaninate, DL-N-(2,6-dimethylphenyl)-N-(2'-methoxyacetyl)alanine methyl ester, N-(2~6-dimethylphenyl)-N-~hlnroRcetyl-D~L-2-amino-butyrolactone, DL-U-(2,6-dimethylphenyl)-N-(phenylacetyl)alanine methyl ester, 5-methyl-S-vinyl-3-(3,5-dichloro-45 phenyl)-2,4-dioxo-1,3-~Y~7oli~inr~, 3-t3~5-dichlorophenyl-(5-meth yl-5 Lhu~y Lhyl]-1,3-~Y~ 701 i ~ i nD-2, 4-dione, 3-(3,5-dichloro-phenyl)-l-isopropylcR ' ,ylhydantoin, N-(3,5-dichloro-0o50~448g6 2 1 9 1 9 9 9 .

38phenyl)-1,2-dimethylcycluyLvydl~s 1,2-~;rArhnJrimirlr~, 2-cyano-[N-ethyl n~ -~b~yl-2-melhor;minolacetamide~
1-12-(2,4-dichlorophenyl~pentyl]-1~-1,2,4-triazole, 2,4-difluoro-~~ 1,2,4-triazoLyl-l-methyl)b~nzl.ydLyl alcohol, 5 N - (3-chloro-2,6-dinitro-4-trifluoromethylphenyll-5-trifluoro-methyl-3-chloro 2 'nopyridine, 1-((bis(4-fl~vLupll~l.yl)methyL-silyl1methyl)-1~-1,2,4-triazole, strobilurins such as methyl ~ ~ minr~[rl_(o-tolyl-10 oxy)-o-tolyllacetate, methyl E-2-{2-t6-(2-cyAn~~ n~ry)pyrimi din-4-yloxy]phenyl}-3-methoxyacrylate, methyl E-methox-imino~o-(2,5-dimethoxy)-c-tolyllacetamide.

~nilinopyrimidines such as N-(4,6-dimethylpyrimidin-2-yl)aniline, 15 N - ~ 4-methyl-6-(L-propynyl)pyrimidin-2-yllaniline, N - ( 4-methyl-6-cyclopropylpyrimidin-2-yl)aniline.

Phenylpyrroles such as 4-(2,2-difluoro-1,3-b~n70rl;oxol-4-yl)pyr-role-3-carbonitrile.
C;nn: dr~ such as 3-(4-chlorophenyl)-3-(3,4-dimethoxy-phenyl)acrylic acid morpholide.

Synthesis examples The ~uLou.luLes given in the synthesis examples below can be used with modification of the starting ~ ~,u~--ds to obtain further L~yleserLatives of the ~ ~ullds I~ and I. The physical data of the ~uLL~ul-dingly prepared products are given in the tables 30 attached in each case.

Example 1 L-Valine (2-methyl-2-(4-methylphenylhydrazide) ~sic]

10 ml of trifluoroacetic acid were added with cooling to 1 g (3 mmol) of N~ ku~o~arbonyl)-1-valine (2-methyl-2-(4-methylphenyl)hydrazide [sic] and the mixture was subse-r~uently stirred at O-C for one hour. It was then warmed to 20 C, 40 the trifluoroacetic acid was largely removed by distillation and the residue was taken up in dichloromethane. ~he organic phase was washed in each case with 40 ml of 10~ strength by weight sodium hydroxide solution and water and dried. The solvent was then removed. 0.7 g of L-valine 2-methyl-2-(4-methylphenylhydra-45 zide) ~sic] remained, which was used in the following stage with-out puri~ication.

0050r44896 2 I 9 I 9 9 9 The i--l ';ates IV of the type [sicl listed in the following table were preeared in a similar manner.

Table 7 ;

H CH ~ Rs R6 ~ - N - C - C -~N - N - R7 ~~ R5 R6 R7 M.p. ~ C)/IR tcm-l) 1 H CH3 4-Cl-C6H4 oil 2 H CH3 4-CH3-C6B4 oil 3 H C2H5 4-Cl-C6H~ 3245,2964,2934,2872,1669,1493 4 H CH~cH3)z 4-CH3-C6B4 3250,2963,2931,2871,1673,1512 ~xample 2 NQ-(sec-~u~u~yo~LLu~lyl~-~-valine 2-methyl-2-~4-methylphenyl)-hydrazide 0.39 g (2.9 mmol) of sec-butyl chluLufoL-,,dLe was added dropwise at 0 C to 0.7 g ~3 mmol) of L-valine 2-methyl-2-(4-methyl-phenyl)hydrazide and 0.32 g (3.2 mmol) of triethylamine in 10 ml of toluene. After 15 hours at 20 C, the organic phase was washed in each case with 20 ml of 10% strength by weight hydrochloric acid, sodium l,~dluJ~,c~rh~n~te solution and water. The organic phase was dried and the solvent was then removed. 0.6 g of the title compound remained as an oil (compound 6 in Table 6).

~xample 3 N"-(LeLL ~u~y~.rbonyl)-1-valine 2-methyl-2-(4-chloro-phenyl)hydrazide S g (o~os mol) of triethylamine were added dropwise at -15 C to 10.9 g (0.05 mol) of Ce~-b~Lu~y~b~.,yl-L-valine in 200 ml of dimethyl~ d~ and the whole was ~h~e~ n~ly stirred for 15 minutes. 6.8 g (0.05 mol) of isobutyl chloroc~rh~n~to were then added and the mixture was left for 10 minutes at -15 C. 7 8 g (0.05 mol) of N-methyl-N-(4-chlorophenyl)hydrazine in 50 ml of dimethylformamide were then added to this solution. ~t was subse-0~50/44896 219199~
40~uently stirred at -15~C for 1 hour and the reaction mixture was left at 20 C for a further 2 hours. ~he solvent was then removed by distillation, the residue was taken up in ethyl acetate and the organic phase was washed in EUCc~Csion in each case with 5 10 ml of 5% ~trength by weight citric acid, 5~ strength by weight sodiu~ 1~d u~ Ate solution and water. The organic phase was dried and .o~l~eY.LL-Led, and the residue which remained was .L , -LoyL~hcd on silica gel ~methyl ~er~ ~u~yl ether:n-hexane =
1:1). 5.5 g of the title compound were obtained as an orange-red 10 resin (compound 27 in Table 6).

Example 4 ~ tert-~utoxycarbonyl)-L-valine 2-methyl-2-~4-methyl-15 phenyl)hydrazide 5.1 g (0.051 mol) of triethylamine and then, at O-C, 8.31 g (0.051 mol) of diethyl uy~r~ph~ te were added t~ a solution of 10.85 g (0.05 mol) of N-t~.L buLu~y.~Lbullyl-L-valine and 20 5.95 g ~0.05 mol) of 4-methylphenylhydrazine in 100 ml of tetra-hydrofuran. The mixture was stirred at O~c for one hour and at 20 C for a further 15 hours, and after removing the solvent the residue was taken up with ethyl acetate. The organic phase was washed in each case with 40 ml of 10% strength by weight sodium 25 hydroxide solution, 10% strength by weight hydrochloric acid, saturated sodium l.ydlug~ ., Ate solution and water. The organic phase was dried and the solvent was then removed. 9.8 g of N~-(telL buLu~yualbullyl)-L-valine 2-~4-methylphenyl)hydrazide remain (m.p.: 163-164-C, compound 21 in Iable 6).
0.48 g (3.4 mmol) of methyl iodide and 0.47 g (3.4 mmol) of potassium carbonate were added at 20-C to 1 g (3.1 mmol) of this compound in 10 ml of dimethy1 forr~ , The mixture was left at this t~ , ~LuLe until starting compound was no longer detectable 35 and the solvent was then removed by distillation. The residue was taken up in ethyl acetate. The organic phase was washed with water, dried and conce~ d~ed. The oil which remained was chroma-tographed on silica gel (cy~7nh~Y~n~:ethyl acetate = 2:1) and 0.3 g of the title oompound was obtained as a yellow oil (com-40 pound 28 in Table 6).

~. 0050/44896 ' ' 2 ~ g 1 9 g 9 -Table 8 5O H R3 ~ R5 R5 R~ - O - C - N - C - C - N - N - R7 H

No. Rl Rl Rs R5 R7 M-p-(~C)/
rR (c~
1 C(CH3)3 CH~Call2 M CH3 C6H5 108 15 2 CH(CH3)2 CHICH312 H Ca3 C6H5 115 3 C6Hs CHICH3lz E CE33 C6H5 138-140 4 CR(CH3)2 CH~CH312 M CH3 4-CH3-C6N4 118-120 C6Hs CH(CH3,l2 H CH3 4-CH3-C6H4 154 6 Ch(cH3)c2Hs CH(CH3)2 H CH3 4-CH3-C5H4 20 7 CH2CH(CH3)2 CH(CH3)2 H CM3 4-CH3-C6H4 oil 8 CH2C6H5 CH(CH3)2 H CH3 4-CH3-C6H4 163 9 cn(cH3)2 CH(CH3)2 H CH3 4-Cl-C6Hc 154 C6H5 CH(CH3)2 H CH3 4-Cl-C6H~ 178-180 25 11 CH2C6Hs CH(CH3)2 H CH3 4-Cl-C6H4 161 12 C(CH3)3 CH(CH3'2 H C2H5 4-CE3-C6H4 84-86 13 CH(CH3)2 CH(CM3 2 H CzH5 4-CH3-CGH4 137-139 14 CH(CH3)C2H5 CHICH3 2 H C2H5 4-CH3-C6H4 118-120 30 15 C(CH3)3 CHICH3 2 H C2H5 4-Cl-C6H4 156 16 CH(CH3)2 CHIcH3t2 H C2H5 4-cl-c6H4 163-165 17 CH~CH3lC2H5 CHfCH3 2 H C2M5 4-Cl-C6~4 168 18 CH CH3 2 CH CH3 2 H CH(CH3)2 4-CH3-C6H~ 118-12035 19 CH CMI,C2H5 CH CH3l2 H CH(CH3)2 4-CH3-C6H4 124-126 CtCH313 CH,CH3t2 H H 4-CL-C6H4 162 21 CICH~3l3 CH~CH3 2 H E 4-CH3-C6B4 163-164 22 CE2CHtCH3)3 CHICH3l2 H CH3 4-cl-C6H4 133 23 C(CH3~3 CHICH3 '2 H H 4-CH30-C6H4 171 24 CICH3 3 CH~,CH3 2 H CM2CH(CE33)2 4-cl-c6H4 171 CICH3l3 CH(cH3)2 El CH2CH(CH3)z 4-CH3-C6H4 154-185 26 C~,C~3l3 CH(CH3)2 H C6H5 C6H5 189-193 27 C(CH3)3 CH(CH3)2 H CH3 4-Cl-C6H~ 2) 45 28 C(CH3)3 CH(CE3~2 H CH3 4-CH3-C6H~ 3) 29 C(C~3~3 CH(CH3)2 H CH(CH2CH3)2 4-CH3-C6H4 130 oo50/44896 2 1 9 ~ ~ 9 9 ~ 42 No. Rl R3 Rs R6 R7 M-p-(~C)/
IR (cmr C CH3 3 CH,CH3)2 M ~CH2~3CH3 4-CH3-C6H4 137-139 31 CICH3l3 CH CH3 2 H cyclo-C5H9 4-CH3-C6H~ 141-142 32 CICH3~3 Ca~CH312 H (CH2)3cH3 4-cl-c6H4 160-161 33 C CH3 3 CHICH3)2 H cyclo-C5Hg 4-cl-c6H4 164-166 34 C~CH3)3 CHICH3)2 H CE{2c6Hs 4-Cl-C6Hg 168-172 CE(CH3~2 CH(CH3)2 H CH2-C6HS 4-Cl-C6H4 171-173 10 36 CH(CH3)C2H5 CH(CH3)2 H CH2-C6H5 4-cl-c6H4 161-171 37 CH(CH3)2 CH(CH3)2 H cyclo-C5H9 4-Cl-C6Hg 221-223 38 CH(CH3)2 CEI~CH3)2 H (CH2)3c~3 4-Cl-C6H~ 193-194 39 CH(CH3)C2Hs CH(CH3)2 H (CH2)3CH3 4-Cl-C6Hg 166-168 lS 40 C(CH3)Z CHlcH3)2 H C(CH3)2 4-C1-C6EI 152 41 CHICH3~2 CH~CH3 2 H CH(CH3)C2Hs 4-Cl-C6H 162 42 CH CH3~C2Hs CHICH312 M CH(CH3)C2Hs 4-Cl-C5H4 136 43 CHICH3l2 CH(CH3 i H cyclo-C6H11 4-CH3-C6H4 193-195 20 44 CHICH3l2 CH(CH312 H (CH2)3cH3 4-CH3-C6H 176-177 CHICB3)C2H5 CH(CH3 ~2 H (CH2)3CH3 4-CH3-C6H4 142 46 C(CH3)3 CH(CH3 2 H CH(CH3)2 4-CH3-C6H4 139 47 CH(CH3)2 CH(CH3 '2 H cyclo-C5H9 4-CH3-C6H~ 188 48 CH(CH3 CzHs CH~CH3 2 H cyclo-C5H9 4-CH3-C6Hg 160 25 49 CH(cH3 '2 CH CH3 2 ~ CH2-C6HS 4-CH3-CsH4 146-148 SO CH(CH3 2 CH~CH3 2 H cyclo-C6H11 4-CH3-C6H4 216 51 C(CH3)3 CHICH3 2 H (CH2)3CH3 4-CH30-C6H4 oil 52 C(CH3)3 CHICH312 H cyclo-C5H9 4-CH30-C6Hg 130-132 30 53 CH(CH3)2 CH(CH3)2 H cyclo-C5H9 4-CH30-C6H~ 172-175 54 CH(CH3)2 CH(CH3l2 H ~CH2)3CH3 4-CH3O-C6H4 158-160 CH(CH3)C2H5 CH(CH3l2 H Cyclo-csH9 4-CH3O-C6Bg 161 56 CH(CH3)C2Hs CH(CH3 2 H (CH2)3Ca3 4-CH3O-C6Hg 128-130 35 57 CH(CH3)2 CH(cH3l2 H CH(CH3)2 4-CH3-C6H4 160 S8 CH(cH3)c2Hs CH(C83 2 H CHz-C6H5 4-cH3-c6H4 139 59 CH(CH3)2 CH(CH3)2 H CH(C2Hs)2 4-CH3-C6H4 oil CH(CH3)2 CH(CH3)2 H C2H$ cyclo-C6H11 173-17S

I) IR (cmrl): 3280, 2969, 293S, 1674, lS15, 1243 2) lH-NMR (CDC13): 0.98 (dd,2H); 1.4 (s,SH); 2.12 (m,l~); 3.8 (s,3EI); 3.95 (t,lEl~; 5.35 (d,lH,~H); 6.8 (d,2H); 7.18 (d,2H) 3) lH-NMR (CDC13): 1.98 (dd,6H); 1.4S (s,9H); 2.13 (~,lH); 2-25 (s,3El); 3.12 (s,3H); 3.87 (t,lH); 5.2 (d,lH,NH); 6.74 (d,2H);
7.00 (d,2H); 8.13 ~s,lH,~H) 0050,44896 2 1 9 1 9 9 9 Table 9 Wl ~ H ~3 ~ R5 R6 \ ~ T
C=N----O----C--~--C--C--~--W--R7 lq2 ~1 No . Wl w2 R' Rs R6 R7 M.p. ~~C ) 1 CH3 c~3 CH(C~3)2 H Ch3 4-Cl-C5H4 104 Z CH3 c~3 CH~CH3~2 H CH3 4-CH3-C6H~ 84 15 Use example5 It was possible to show the ~ungicidal action of the ~ ' of the general formula I by the following te3ts:

The active ~ d., were prepared as a 20% strength by weight Dlmulsion in a mixture of 70% by weight of cyr-lr~hr~YRnr~l, 20% by weight of WekanilD LW (Lutensol'~ AP6, wetting agent with emulsi-~ier and dispersant action based on ethoxylated alkylphenols) and 10~ by weight of Emulphor~ EL (Emulan~ EL, c lc;~;r7r based on ethoxylated fatty alcohols) and diluted with water according to the desired cu~ ,,LL~ion.

Plasmopara viticola Leaves of potted vines of the variety ~uller-Thurgau were sprayed with aqueous spray liquor which contained 80% by weight of active compound and 20% by weight of emulsifier in the dry substance. In order to assess the duration of action of the active ~ , ' , the plants were placed in a greenhouse for 8 days after the spray coating had dried on. Only then were the leaves infected with a ~ospore sncpDncion of Plasmopara viticola (vine PeLVLIU~UL L). The vines were first placed for 48 hours in a chamber containing water vapor-saturated air at 24~C and then for 5 days in a green-40 house at from 20 to 30'C. After this time, the plants were placedin the moist chamber again for 16 hours to accelerate escape from the spor~ngiorhr~re~ The extent of fungal outbreak on the bottoms of the leaves was then assessed visually.

. 0050/44896 ~ 44 In this test, the plants treated with an aqueous preparation con-taining 250 ppm of the ~ ~c 4, 6, 9, 10, 12, 13, 14, 15, 16, 17, 18, 19, 20 and 22 from Table 6 in each case showed a maximum attack o~ 15*, while ul,LL~aLed plants were attacked to 70~.

Claims

We claim:

1. A carbamoylcarbohydrazide of the general formula I

or its salts, where the radicals have the following meanings:

R1 is C1-C8-alkyl, C2-C8-alkenyl or C2-C8-alkynyl, it being possible for these radicals to be partly or completely halogenated and/or to carry one to three of the following groups: cyano, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkoxycarbonyl, C3-C7-cycloalkyl, C3-C7-cycloalkenyl, aryl, aryloxy and heteroaryl, it being possible for the cyclic radicals in turn to carry one to three of the following substituents: halogen, cyano, C1-C4-alkyl, C1-C4-alkoxyalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkoxycarbonyl, aryl, aryloxy and heteroaryl, C3-C7-cycloalkyl or C3-C7-cycloalkenyl, it being possible for these radicals to be partly or completely halogenated and/or to carry one to three of the following groups:
cyano, C1-C4-alkyl, C1-C4-alkoxyalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C14-haloalkxy, C1-C4-alkylthio, C1-C4-alkoxycarbonyl, aryl, aryloxy and aryl-(C1-C4)-alkyl, it being possible for the cyclic groups to carry one to three of the following substituents: halogen, cyano, C1-C4-alkyl, C1-C4-alkoxyalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkoxyoarbonyl, aryl and aryloxy, a non-aromatic 4-to 8-membered ring, which, as ring members, in addition to carbon can also containg one or two of the heteroatoms oxygen, sulfur and nitrogen, it being possible for the carbon atoms in the ring to carry one or two of the following groups: halogen, cyano, C1-C4-alkyl, C1-C4-alkoxyalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkoxycarbonyl, aryl and aryloxy and the second and each further nitrogen atom as a heteroatom in the ring carrying hydrogen or a C1-C4-alkyl group, aryl or heteroaryl, it being possible for there radicals to carry one to three of the following groups: halogen, cyano, C1-C4-alkyl,C1-C4-alkoxyalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkoxycarbonyl, aryl, aryloxy and heteroaryl, in which the cyclic substituents in turn can carry one to three of the following substituents: halogen, cyano, C1-C4-alkyl, C1-C4-alkoxyalkyl, C1-C4-haloalkyl, Cl-C4-alkoxy, C1-C4-alkoxy, C1-C4-alkylthio and C1-C4-alkoxycarbonyl or W1W2C=N-, where W1 is C1-C8-alkyl which can be partly or completely halogenated and/or can carry one to three of the following groups: cyano, C1-C4-alkoxy, C1-C4-halo-alkoxy, C1-C4-alkylthio, aryl, aryloxy and hetexo-aryl, it being possible for the cyclic groups in turn to carry one to three of the following substituents:
halogen, cyano, C1-C4-alkyl, C1-C4-alkoxyalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alky1thio, C1-C4-alkoxycarbonyl, aryl and aryloxy, C2-C8-alkenyl or C2-C8-alkynyl, it being possible for there radicals to be partly or completely halogenated and/or to carry one to three of the following groups:
cyano, C1-C4-alkoxycarbonyl, C1-C4-haloalkoxy, C1-C4-alkyl-thio, C1-C4-alkoxycarbonul, aryl and aryloxy, it being possible for the cyclic groups in turn to carry one to three of the following substituents: halogen, cyano, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkyl-thio, C1-C4-alkoxycarbonyl, aryl and aryloxy, C3-C7-cycloalkyl or C3-C7-cycloalkenyl, it being possible for these radicals to carry one to three of the following groups: halogen, cyano, C1-C4-alkyl, C1-C4-alkoxyalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4--haloalkoxy, C1-C4-alkylthio,C1-C4-alkoxy-carbonyl, aryl and aryl-(C1-C4)-alkyl, it being possible for the groups which contain aryl to carry one to three of the following substituents: halogen, cyano, C1-C4-alkyl, C1-C4-alkoaxyalkyl, C1-C4-halo-thio, alkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkoxycarbonyl, aryl and aryloxy or aryl or heteroaryl, it being possible for these radicals to carry one to three of the following groups: halogen, cyano, C1-C4-alkyl, C1-C4-alkoxy-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkoxycarbonyl, aryl and aryloxy and W2 is hydrogen or one of the groups W1:
R2 is hydrogen or C1-C8-alkyl or C3-C7-cycloalkyl, which can be partly or completely halogenated;
R3 is hydrogen or C1-C8-alkyl, it being possible for this radical to carry one to three of the following groups: halogen, cyano, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio and C1-C4-alkoxycarbonyl, C3-C7-cycloalkyl or phenyl-(C1-C4)-alkyl, it being possible for the rings of these radicals to carry one to three of the following groups: halogen, cyano, C1-C4-alkyl, C1-C4-alkoxyalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkoxycarbonyl, aryl and aryloxy;
R4 is hydrogen or one of the radicals R3 or R3 and R4, together with the C atom to which they are bonded, are a 4- to 8-membered ring which, as ring members, in addition to carbon can also contain one or two of the heteroatoms oxygen, sulfur and nitrogen, it being possible for the carbon atoms in the ring to carry onr or two of the following groups: halogen, cyano, C1-C4-alkyl, C1-C4-alkoxyalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C1-C4-alkoxycarbonyl, aryl and aryloxy and nitrogen as a heteroatom carrying hydrogen or a C1-C4-alkyl group;
R5 is one of the radicals R2;
R6 is C1-C8-alkyl, C2-C8-alkenyl or C2-C8-alkynyl, it being possible for these radials to be partly or completely halogenated and/or to carry onr to three of the following groups: cyano, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, C3-C7-cycloalkyl, C3-C7-cycloalkenyl, aryl, aryloxy and heteroaryl, it being possible for the cyclic radicals in turn to carry one to three of the following substituents: halogen, cyano, C1-C4-alkyl, C1-C4-alkoxyalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, aryl, aryloxy and heteroaryl, C3-C7-cycloalkyl or C3-C7-cycloalkenyl, it being possible for these radicals to be partly or completely halogenated and/or to carry one to three of the following groups:
cyano, C1-C4-alkyl, C1-C4-alkoxyalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, aryl, aryloxy and aryl-(C1-C4)-alkyl, it being possible for the cyclic groups to carry one to three of the following substituents: halogen, cyano, C1-C4-alkyl, C1-C4-alkoxyalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, aryl and aryloxy, a non-aromatic 4- to 8-membered ring, which, as ring members, in addition to carbon can also contain one or two of the heteroatoms oxygen, sulfur and nitrogen, it being possible for the carbon atoms in the ring to carry one or two of the following groups: halogen, cyano, C1-C4-alkyl, C1-C4-alkoxyalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkyltio, aryl and aryloxy and the second and each further nitrogen atom as a heteroatom in the ring carrying hydrogen or a C1-C4-alkyl group, aryl or heteroaryl, it being possible for these radicals to carry one to three of the following groups: halogen, cyano, C1-C4-alkyl, C1-C4-alkoxyalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, aryl, aryloxy and heteroaryl, in which the cyclic substituents in turn can carry one to three of the following substituents: halogen, cyano, C1-C4-alkyl, C1-C4-alkoxy-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy and C1-C4-alkylthio or if R3 is isopropyl, hydrogen;
R7 is one of the radicals R6, excluding hydrogen;
X1 is oxygen of sulfur, X2 is oxygen or sulfur, X3 is oxygen or sulfur;

excluding the compounds according to the following definition of the radicals:

Ia-d (R1 = Ph-CH2; R2 = H; R3 = CH3, (CH2)2CH3, CH(CH3)2 or Ph-CH2; R4,R5 = H; R6,R7 = CH2CH2Cl), Ie-h (R1 = C(CH3)3; R2 = H; R3 = CH3, CH(CH3)2, CH(CH3)CH2CH3, CH2CH(CH3)2 or Ph-CH2; R4,R5 = H;
R6,R7 = CH2CH2Hr), Ii (R1 = Ph-CH2; R2 = H; R3 = CH3; R4,R5 = H;
R6 = CH3; R7 = Ph), Ij-k (R1 = Ph-CH2; R2; = H; R3 =CH(CH3)2 or CH2CH(CH3)2; R4,R5 = H; R6,R7 = Ph), Il (R1 = C(CH3)3; R2 = H; R3 = CH(CH3)2;
R4,R5,R6 = H; R7 = Ph), Im (R1 = Ph-CH2; R2 = H; R3 = Ph-CH2; R4, R5 = H;
R6,R7 = CH2CH3), In-o (R1 = Ph-CH2; R2 = H; R3 = CH2SCH3 or CH2CH2SCH3;
R4,R5 =H; R6, R7 = CH2CH2Cl) and further excluding the following compounds I in which x1 = O, X2 = O, R2 = H, X3 = O, R4 = H and R5 = H and the radicals R1, R3, R6 and R7 are No. R1 R3 R6 R7 Ip phenyl-CH2 CH2(4-F-C6H4) CH2CH2Cl CH2CH2Cl Ig phenyl-CH2 CH2(3-F-C6H4) CH2CH2Cl CH2CH2Cl Ir phenyl-CH2 CH2(2-F-C6H4) CH2CH2Cl CH2CH2Cl Is phenyl-CH2 (CH2)2COOC2H5 CH2CH2Cl CH2CH2Cl It phenyl-CH2 CH2C6H5 CH2CH2Br CH2CH2Br Iu tert-butyl CH2CH2SCH3 CH3 CH3 Iv phenyl-CH2 CH2C6H5 CH3 CH3 Iw phenyl-CH2 CH2C6H5 CH3 C6H5 Ix phenyl-CH2 CH2C6H5 CH2CH2I CH2CH2I
Iy phenyl-CH2 CH(Cl)C6H5 CN2CH2Cl CH2CH2Cl Iz phenyl-CH2 CH2CH2COOH C6H5 C6H5 Iaa phenyl CH2 CH(CH3)2 H C6C5

2. A process for preparing carbamoylcarbohydrazides of the general formula I or their salts as claimed in claim 1, which comprises reacting a carbamoylcarbohydrazide of the general formula II

with a hydrazine of the general formula III

and if desired converting the compound I thus obtained to one of its salts in a manner known per se.

3. A process for preparing carbamoylcarbohydrazides of the general formula I in which R1 is a group W1W2C=N-, or their salts as claimed in claim 1, which comprises converting a carbamoylcarbohydrazide of the general formula I

where X1, X2 and X3 are in each case oxygen, and the group R1-X1-(CO) represents a protective group which can be removed in a manner known per se, to an amino acid hydrazide IV

reacting the amino acid hydrazide IV thus obtained with a chloroformyl oxime of the general formula V

in the presence of a base and if desired converting the compound I thus obtained to one of its salts in a manner known per se.

4. A process for preparing carbamoylcarbohydrazides of the general formula I or their salts as claimed in claim 1, in which R6 is C1-C8-a1ky1, C4-C7-cycloalkyl or aryl-(C1-C4)-alkyl, which comprises reacting a carbamoylcarbohydrazide of the general formula I as claimed in claim 1, in which R6 is hydrogen, with a compound of the general formula R6-X, in which R6 is C1-C8-alkyl, C4-C7-cycloalkyl or aryl-(C1-C4)-alkyl and X is a negative leaving qroup, with additional use of a base and if desired converting the compound I thus obtained to one of its salts in a manner known per se.

5. A composition suitable for controlling harmful fungi, containing customary additives and an effective amount of compound of the general formula I or one of its salts as claimed in claim 1, excluding the compounds Ia to Iaa.

6. A process for controlling harmful fungi, which comprises treating the harmful fungi, their environment or the plants, surfaces, materials or spaces to be kept free from them with an effective amount of a compound of the general formula I or one of its salts as claimed in claim 1, including the compounds Ia to Iaa, or a composition containing I as claimed in claim 5.

7. The use of the compounds of the general formula I or of one of their salts as claimed in claim 1, including the compounds Ia to Iaa, for controlling harmful fungi.

8. An amino acid hydrazide of the general formula IV

where X3 is oxygen and R3 is a group CH(CH3)2, CH2CH(CH3)2 or CH(CH3)C2H5 and R4, R5, R6 and R7 have the meaning given in claim 1, excluding the compounds according to the following definition of the radicals:
IVa-b (R3 = CH(CH3)2; R4,R5 = H; R6,R7 = CH2CH2Cl).
IVc-e (R3 = CH(CH3)2, CH(CH3)CH2CH3 or CH2CH(CH3)2;
R4,R5 = H; R6,R7 = CH2CH2Br), IVf (R3 = CH(CH3)2; R4,R5,R6 = H; R7 = Ph), IVg (R3 = CH(CH3)2; R4,R5 = H; R6,R7 = Ph).

9. An amino acid hydrazide of the general formula IV as claimed in claim 8, in which R3 is a group CH(CH3)2, R4 and R5 have the meaning given in claim 1, R6 is C1-C8-alkyl, it being possible for this radical to be partly or completely halogenated and/or to carry one to three of the following groups: cyano, C1-C4-alkoxy, C1-C4-haloalkoxy C1-C4-alkylthio, C3-C7-cycloalkyl, C3-C7-cycloalknyl, aryl, aryl, aryloxy and heteroaryl, it being possible for the cyclic radicals in turn to carry one to three of the following substituents: halogen, cyano, C1-C4-alkyl, C1-C4-alkoxyalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, aryl, aryloxy and heteroaryl and R7 is aryl, it being possible for this radical to carry one to three of the following groups: halogen, cyano, C1-C4-alkyl, C1-C4-alkoxyalkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy, C1-C4-alkylthio, aryl, aryloxy and heteroaryl, in which the cyolic substituents in turn can carry one to three of the following substituents: halogen, cyano, C1-C4-alkyl, C1-C4-alkoxy-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkoxy and C1-C4-alkylthio.