DD213126A5 - SCHAEDLINGSBEKAEMPFUNGSMITTEL - Google Patents

Abstract

The present invention relates to pesticides containing novel substituted malonic acid derivatives of the formula I in which R is high-R 4, as defined in the description, as active ingredients.

Description

- /} - Bariin, 20.9.1983

62 318/11

Pesticides Applic ungs Field of the Invention

The present invention relates to the use of substituted malonic acid derivatives as pesticides »

Ch ar aktsJTlSt Ik ₁ the known technical solutions

It has already been disclosed that carbamates such as 5,6-dimethyl-2-dimethyla! 4-amino-4-pyrimidinyl-dimethylcarb! T) 3t or 1-naphthyl-N-ethylcarbaraat possess insecticidal activity (US Pat. No. 3,493,574, US Pat PS 2 903 478). Its effect is not always satisfactory when it comes to low levels of supplementation »

the invention

Surprisingly, the substituted malonic acid derivatives of the invention exhibit a considerably higher insecticidal action than those known from the prior art carbamates of the same direction of action such as 5,6 ~ dimethyl ~ 2-dimethyl '~ amino-4-pyrimidinyl dimethylcarbamate or l ~ ~ N * naphthyl -rnethylcarbamate (U.S. Patent 3,493,574 and U.S. Patent 2,903,478),

Explanation of the essence of the invention

It has been found that the substituted malonic acid derivative of the general formula I is outstandingly suitable for controlling pests.

damping are: R ¹ - C O - R ² : - CO R ³ ^ CO - R ⁴ in which he

R is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, which may be optionally substituted

R is hydrogen, trialkylsilyl and alkyl,

5. cycloalkyl, alkenyl, alkynyl, aralkyi, alkyl

carbonyl, arylcairbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulfenyl, arylsulfenyl, alkylsulfonyl, arylsulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, arylalkylaminosulfonyl, optionally substituted with

may be tuiert, as well as for radicals of the formula

- CO - NR ⁵ R ⁶

stands, where

R and R independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, alkylaminocarbonyl, arylaminocarbonyl, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulfonyl, arylsulfonyl, where these radicals may optionally be substituted,

4 R ^and 3-R "independently represent the radicals

Amino, OX where X is hydrogen, optionally substituted alkyl or cycloalkyl, aralkyl and one equivalent of alkali or alkaline earth,

3 4

furthermore, R and R "are alkylamino, aryl

amines, aralkylamines, dialkylamino, cycloalkylamino, alkenylamines, trialkylsilylamino, trialkylsilylalkylamino, nitrogen-containing

Le A 22 012.

saturated heterocyclic radicals optionally containing further heteroatoms, wherein the

Radicals may optionally be substituted, R-7

3 4 furthermore R and R are radicals of the formula

NHR

in which

R is hydroxyl, formyl, alkylcarbonyl, alkenylcarbonyl, cycloalkenylcarbonyl, arylcarbonyl, amino, alkylamino, arylamino, alkylarylamino, dialkylamino, alkylaminocarbonylamino

Il

(-NH-C-NH-alkyl), Alkylaminothiocarbonylamino S

Il

(-NH-C-NH-alkyl), arylaminocarbonylamino, arylaminothiocarbonylamino, alkylcarbonylamino O

(-NH-C-alkyl), arylcarbonylamino, alkylsulphonic

fonylaminocarbonylamino (-NH-C-NH-SO ^ -alkyl),

Arylsulfonylaminocarbonylamino, alkylcarbonyl

0 0

Il K

aminocarbonylamino (-NH-C-NH-C-Aikyl), Arylcarbonylaminocarbonylamino wherein the .Alkyl or aryl radicals may be optionally substituted,

4 R and R * furthermore represent radicals of the formula

-NH-N = C

in which

Le A 22 012

R is alkyl or aryl which may be optionally substituted, and

R is hydrogen or alkyl,

2 3 4

when R is hydrogen, R and R may not simultaneously be amino.

Particularly suitable are the substituted malonic acid derivatives which can be used according to the invention for controlling insects and spider mites. They are characterized by a significantly better effect than the known from the prior art for these indications compounds. They also have favorable levels of warm-blooded toxicity,

Preference is given here to the new compounds of the formula I mentioned below as being preferred.

1. The novel substituted malonic acid derivatives of general formula I have also been found

^ 0 - R ²

R ³ -C-CO-R ³ I

^ CO - R ⁴

in which

R is alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroalkyl, the given

if they can be substituted stands

R is hydrogen, trialkylsilyl and

Alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, alkylcarbonyl, arylcarbonyl, alkoxy

Le A 22 012

carbonyl, aryloxycarbonyl, alkylsulfenyl, arylsulfenyl, alkylsulfonyi, arylsulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, arylalkylaminosulfonyl, which may optionally be substituted, as well as radicals of the formula

-CO-NR ^b R

stands, where

R and R independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, alkylaminocarbonyl, arylaminocarbonyl, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulfonyl, arylsulfonyl, where these radicals may optionally be substituted,

4 R and R independently of one another represent the radicals amino, OX where X is hydrogen, optionally substituted alkyl or cycloalkyl, aralkyl and one equivalent of alkali or alkaline earth metal,

3 4 furthermore R and R are alkylamino,

Arylamines, aralkylamino, dialkylamino, cycloalkylamino, alkenylamino, trialkylsilylamino, trialkyisilylalkylamino, nitrogen-containing saturated heterocyc

lische radicals optionally containing further heteroatoms, wherein the radicals may be optionally substituted,

Le A 22 012

3 4 furthermore R and R are radicals of

formula

-NHR ⁷

in which

7 R for hydroxyl, formyl, alkylcarbonyl, Al

kenylcarbonyl, cycloalkenylcarbonyl, arylcarbonyl, amino, alkylamino, arylamino,

Alkylarylamino, dialkylamino, - alkylamino

! I

carbonylamino {-NH-C-HH-alkyl), alkylamino

thiocarbonylamino (-NH-C-NH-alkyl), aryl-

aminocarbonylamino, arylaminothiocarbonyl

amino, alkylcarbonylamino (-NH-C-alkyl), arylcarbonylamino, alkylsulfonylaminocarbonyl-

ii

amino (-NH-C-NH-SC ^ -alkyl), arylsulfonyl-

aminocarbonylamino, alkylcarbonylamino

0 0.

11 Il

carbonylamino (-NH-C-NH-C-alkyl), arylcarbonylaminocarbonylamino, where the alkyl or aryl radicals may optionally be substituted,

4 R and R furthermore represent radicals of the formula

.R ⁸

-NH-N = C

• R ⁹

Le A 22 012

in which

R is alkyl or aryl optionally

may be substituted and

R is hydrogen or alkyl

R .for hydrogen, R and / or

R * does not stand for amino, OX, where X is alkyl or cycloalkyl;

Preferably in formula I

R ^{1 is} C. Alkenyl, C is cycloalkyl, C _n . _o -

Cycloalkenyl, which may be the same

or may be substituted differently by one or more of the following radicals:

Halogen, in particular fluorine, chlorine, bromine, C _1. -Alkoxy, in particular metlioxy or

Ethoxy, carboxyl, carbalkoxy, in particular methoxycarbonyl or ethoxycarbonyl, phenyl, phenoxy, thiophenyl, where the phenyl rings may be substituted by halogen or alkyl;

R is furthermore phenyl which may optionally be identical or different and may be substituted by one or more of the following radicals: halogen, in particular

Chlorine, bromine, fluorine, nitro, amino, OH, CN,

C -_, - alkyl in particular methyl, C ₁ * - haloalkyl in particular trifluoromethyl, trichloromethyl, pentafluoroethyl, C -.- alkoxy, methylenedioxy, ethylenedioxy, C. _A - haloalkoxy, in particular Trifiuor-

Le A 22 012

methoxy, pentafluoroethoxy, Difluorraethylendioxy, halogen-substituted ethylenedioxy, C ₁ _ ₄ ~ alkylthio, C - ^ - halogenoalkylthio, in particular trifluoromethylthio, C_ _O alkoxyalkyl, C ₂ _g-haloalkoxyalkyl, C.. alkyl

sulfonyl, in particular methylsulfonyl, ^C 1-4 -haloalkylsulfonyl, carboxyl, carbalkoxy, in particular methoxycarbonyl, and also the radical C 1 -alkoxy-N =CH-, in particular CH-ON =CH-, furthermore phenyl, phenyloxy,

Thiophenyl which may optionally be substituted by halogen or C ₁ _ ₄ ~ alkyl, as well as for Carboxylalkoxy, 2 - 4 C-Atoraen as carboxymethoxy,

T5 R is furthermore heteroaryl, such as pyridi-

nyl, pyrimidinyl, triazinyl, isoxazolyl, thiazolyl, oxadiazolyl, imidazolyl, triazolyl, furanyl, thiophenyl, which may be monosubstituted or polysubstituted by identical or different halogen, in particular chlorine,

C., -alkyl, in particular methyl, ethyl, C _1-4 -alkoxy, in particular methoxy, ethoxy

may be substituted.

1 R "is also preferred for

3-nitrophenyl, 3-iodophenyl, biphenyl, 4-

Trimethylsilyloxyphenyl, 4-chloro-3-nitrophenyl, 3-chloro-4-nitrophenyl, 3,4,5-trichlorophenyl, 3,5-dichloro-4-fluorophenyl, 4-difluoromethylphenyl, 3-nitro-4-fluoro

3Q phenyl, 3-fluoro-4-nitrophenyl, 3-trifluoro-

methyl-4-chlorophenyl, 4-trifluoromethyl-3-chlorophenyl, 3-chloro-5-trifluoromethylphenyl, 3 , 5-dichloro-4-hydroxyphenyl , 3,4-dichloro-4-methoxyphenyl, 3,5-dichloro-4- aminophenyl, 3- chloro-4-hydroxyphenyl,

Le A 22 012

3,4-di (trifluoromethyl) phenyl, 3-trifluoromethyl-4,5-dichlorophenyl, 4-trifluoromethyl-3,5-dichlorophenyl, 4-trifluoromethoxy-3-nitrophenyl, 4-trifluoromethoxy-3-bromophenyl, 4-nitro 3-trifluoromethoxyphenyl, 4-bromo-3

trifluoromethoxyphenyl, 3-nitro-4-trifluoromethoxy-5-chlorophenyl, 4-methoxy-3,5-dichlorophenyl, 4-methyl-3,5-dichlorophenyl, 4-fluoro-3-bromophenyl, 4-bromo-3-fluorophenyl, 4-chloro-3-methylphenyl, 4-trifluoromethyl

mercaptophenyl, 4-trifluoromethoxy-3-chlorophenyl, 3-trifluoromethyl-4-chlorophenyl, 4-chloro-difluoromethoxy-3-chlorophenyl, 4-fluoro-3-chlorophenyl, pentafluorophenyl, 4-fluoro-3,5-dibromophenyl, 4- fluoro-3-chloro-

5-bromophenyl, 4-chloro-3,5-dibromophenyl, 4-bromo-3,5-dichlorophenyl, 3-bromo-4,5-dichlorophenyl, 3,4,5-trifluorophenyl, 3,4,5-tribromophenyl.

Preferably, in the formula I

2 R is hydrogen, trialkylsilyl with 1-4

Carbon atoms in the alkyl moiety, C. _1-alkyl, C. _{1-alkylcarbonyl,} benzoyl which is optionally sub same or different by one or more of the following groups (A)

(A) is halogen, in particular chlorine, bromine, fluorine, nitro, amino, CN, C ₁ _- alkyl in particular methyl, C ₁ _.- haloalkyl in particular trifluoromethyl, pentafluoroethyl, C _1-4 -alkoxy, C _1-4 ^-

Haloalkoxy, in particular trifluoromethoxy, pentafluoroethoxy, methylenedioxy, ethylenedioxy, difluoromethylenedioxy, halogen-substituted ethylenedioxy, such as tri-

La A 2 2 012

fluoroethylenedioxy, C ₁ -C 4 -alkylthio, C ₁ _.- haloalkylthio especially trifluoromethylthio, C, "-alkoxyalkyl, C" --halogen »

ώ -ο Ζ - ο '

alkoxyalkyl, C.sub.1-4 alkylsulfenyl, phenylsulfenyl optionally substituted

C ₁ -alkylsulfonyl, in particular methylsulfonyl, C 1-haloalkylsulfonyl, carbalkoxy, in particular methoxycarbonyl, and also the radical C _1-4 -alkoxy-N = CH-, in particular CH-ON = CH-,

furthermore phenyl, phenyloxy, thiophenyl, which may optionally be substituted by halogen or C ₁ -alkyl, and by carboxyalkoxy having 2-4 C atoms, such as

5 boxymethoxy;

R is furthermore C 1-4 alkoxycarbonyl,

Phenoxycarbonyl which may optionally be substituted by one or more of the radicals (A), C ₁ -alkylsulfonyl, phenylsulfonyl which may be substituted by

one or more of the groups (A) may be substituted, _{C1 4} alkylaminosulfonyl, C ₁ _ J.- alkyl sulfenyl, phenyl sulfenyl which may optionally be substituted, di-C ₁ _.-alkylaminosulfonyl, phenylaminosulfonyl

which may optionally be substituted by one or more of the radicals (A), phenyl-C-alkyl-aminosulfonyl and for radicals of the formula

Le A 22 012

-C-NR ⁵ R ⁶

in which

R and R independently of one another represent hydrogen, C 1 -C 6 -cycloalkyl, phenyl which is optionally substituted by one or more

of the radicals (A) may be substituted, phenylcarbonyl which may be optionally substituted by one or more of the radicals (A), C ₁ _. _n ~ alkylcarbonyl, C ₄ -alkylaminocarbony1, C-alkoxycarboxylic

carbonyl, phenylaminocarbony1, phenylsulfonyl which may be optionally substituted by one or more of the radicals (A)

stand.

Preferably in formula I

4 R and R are independently of one another amino, C, "amino,

C ₁ -C 4 -alkylamino, C ₁ -C 4 -alkylamino, which may be optionally substituted by hydroxyl, C _1-4 -alkoxy, phenylamino, the ge

optionally substituted by one or more of the above radicals (A) may be substituted, C_ r -Cycloalkylamino, a saturated heterocycle having 5-6 ring carbon atoms such as morpholine, tri-C ₄ -alkylsilylamino, and radicals of the

formula

-NHR ⁷

in which

Le A 22 012

R is C-alkylcarbonyl, C-alkenylcarbonyl, C _n . "Cycloalkenylcarbonyl, such as acetyl, -C. Alkylamino such as methylamino or t-butylamino, phenylamino which may be replaced by one or more

of the radicals (A) given above may be substituted, C ₁ -alkylaminocarbonyl-O

Il

amino (-NH-C-NH-alkyl), phenylaminocarbene

bonylamino (-NH-C-NH-phenyl) optionally substituted by one or more of

Radicals (A) may be substituted, C-i .-

Il

Alkylcarbonylamino (-NH-C-alkyl), benzoylamino, which may optionally be substituted by one or more of the radicals (A), is

3 4 R and R are also a radical

the formula

-NH-N =

in which

R is C ₁ , -alkyl, in particular methyl,

Phenyl which may optionally be substituted by one or more of the radicals (A),

Le A 22 012

R ^{9 is} hydrogen, C _1-4 -Al] CyI.

Particular preference is given to compounds of the formula I in which

R is C 1-6 -cycloalkyl, C 1-6 -alkenyl optionally substituted by carboxyl, and also phenyl which is optionally substituted by halogen, in particular fluorine or chlorine, C _1-4 -alkyl, in particular methyl, C _1-4 -alkoxy, . Haloalkoxy, C - ^ - haloalkyl, NH ₃ , CH ₃ ON = CH-, or nitro is substituted.

Especially to be mentioned are compounds of general formula I in which

R is phenyl which is optionally one to three times the same or different in the 3,4,5-position by halogen, in particular fluorine,

Chlorine, bromine, iodine is substituted,

R is C.. Alkyl in particular methyl, optionally halogen-substituted C ₁ _ ₄ ~ alkylaminosulfonyl, C _1. Alkylcarbonyl, in particular methylcarbonyl optionally substituted by halogen

substituted phenylcarbonyl, phenylsulfenyl, C 1-4 alkylsulfenyl, trialkylsilyl.

Le A 22 012

in particular trimethylsilyl and for

"56 5

-C-NR R, where R is hydrogen

and R is phenyl or phenylcarbonyl optionally substituted by halogen or C ₁ , -alkyl or C ₁ -alkylcarbonyl,

4 R and R are the same or different and for

Amino, trimethylsilylamino, C ₁ _.- alkylcarboxylic

bonylamino especially acetylamino formyl

amino are only then where both radicals R

4 and R are amino if E

Meaning as hydrogen has.

4 2

and R is amino if R is another

Particular mention may be made of compounds of the formula I in which

R is phenyl, if appropriate

mono- or polysubstituted by chlorine and

R is trimethylsilyl,

4 R and R represent trimethylsilylamino.

Le A 22 012

20.9.1983 - 15 - 62 918/11

The new substituted malonic acid derivatives have favorable toxicity and root systemic activity

2t It has also been found that the compounds of the formula I

in which

"J R is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, hetero" "which may optionally be substituted

10

for hydrogen, trialkylsilyl and also alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulfenyl, arylsulfenyl, alkylsulfonyl, arylsulfonyl, alkylaminosulfonyl, dialkylaminosulfonyl, arylaminosulfonyl, arylalkylaminosulfonyl which may optionally be substituted, as well as radicals of the formula

-CO-NR ⁵ R ⁶

stands,

in which

20

R and R independently of one another represent hydrogen,

Alkyl, cycloalkyl, aryl, alkylaminocarbonyl, arylaminocarbonyl, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulfonyl, arylsulfonyl, where these radicals may optionally be substituted,

4 R and R stand independently for the,

Radicals amino, OX wherein X is hydrogen, optionally substituted alkyl or

Le A 22 012

Cycloalkyl, aralkyl and one equivalent of alkali or alkaline earth,

3 4 furthermore R and R are alkylamino,

Arylamino, aralkylamino, dialkylamino, cycloalkylamino, alkenylamino, trialkyl

silylamino, trialkylsilylalkylamino, nitrogen-containing saturated heterocyclic radicals which optionally contain further heteroatoms, it being possible for the radicals to be optionally substituted,

furthermore formula

in which

3 4 furthermore R and R are radicals of

-NHR ⁷

R is hydroxyl, formyl, alkylcarbonyl, Al

kenylcarbonyl, cycloalkenylcarbonyl, arylcarbonyl, amino, alkylamino, arylamino, alkylarylamino, dialkylamino, al-

ti

kylaminocarbonylamino (-NH-C-NH-alkyl), alkylaminothiocarbonylamino

Il

(-NH-C-NH-alkyl), arylaminocarbonylamino, arylaminothiocarbonylamino, alkylcarbonyl · 0

Il

amino (-NH-C-alkyl), arylcarbonylamino, Alky1sulfony1aminocarbonylamino 0

It

{-NH-C-NH-SC ^ -alkyl), arylsulfonylamino

Le A 22 012

- 18 -

carbonylamino, alkylcarbonylaminocarbonyΙΟ 0

amino (-NH-C-NH-C-alkyl), arylcarbonylaminocarbonylamino, where the alkyl or aryl radicals may optionally be substituted,

4 R and R are furthermore radicals of the formula

-NE-i7 = C where

R is alkyl or aryl which may optionally be substituted and

R is hydrogen or alkyl,

2 3

R stands for hydrogen, R and / or

or R not for amino, OX, where X is for

Alkyl or cycloalkyl;

gets by

3 4 a) for the pail, that R and R are not OH,

O-alkali, 0 (alkaline earth) 1/2 stand, compounds of FOrrael II

II

Le A 22 012

O ο ^ O *; ''

in which

4 R, R and R "are as defined above,

₁ ) with compounds of the formula III

R ¹⁰ -Y III

in which

Y is halogen or -O-SO ₂ -OC _1-4 ,

R ^{10 is} alkyl, cycloalkyl, aralkyl, alkenyl, alkynyl, which may optionally be substituted,

translates or

a_) with compounds of the formula IV

IV

in which

Z for kallogen, C-alkylcarbonyloxy, CN,

stands,

Le A 22 012

R is alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulfonyl, arylsulfonyi, alkylaminosulfonyl, dialkylamin sulfonyl, arylaminosulfonyl, arylalkylaminosulfonyl which are optionally substituted and for

-CONR ⁵ R ⁶

stands, where

R, R are identical or different for hydrogen, alkyl, cycloalkyl, aryl, alkyl

carbonyl, arylcarbonyl, alkylsulfonyl, arylsulfonyl, which may optionally be substituted,

translates or

a_) with compounds of the formula VR ¹² -NC0 V

in which

R 12 is alkyl, cycloalkyl, aryl, alkylcarbonyl,

Arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulfonyl, arylsulfonyl, the

may optionally be substituted,

Le A 22 012

translates or

a.) First with compounds of formula VI 0

il

OCW-C-HaI 'VI where Hal is halogen

and then reacted with compounds of the formula VII

(R ¹³ ) ₂ NH (VII)

in which

R independently of one another are hydrogen,

Alkyl or aryl stand

or with water,

b) in the event that R ^{2 is} trialkylsixlyl and R ^w and R are not OH, O-alkali, O (alkaline earth) 1/2, compounds of formula II

(above) with trialkyklysilyl compounds of the formula VIII

Le A 22 012

O. J '* ^{> J} ° O

Alkyl Si-W VIII

in which

W is halogen, CN, or trialkylsilylamino

in approximately equimolar amounts optionally

in the presence of a diluent, if appropriate in the presence of a catalyst and optionally in the presence of an acid acceptor.

3. It has also been found that the compounds of formula IX

IX

in which

R has the meaning given under 1 and

1.5 R for amino, optionally substituted

Alkyloxyo or cycloalkyloxy, further for alkylamino, arylamino, dialkylamino, cycloalkylamino, alkenylamines, nitrogen-containing saturated heterocyclic radicals the given

Le A 22 012

if further heteroatoms contain, where the radicals may be optionally substituted, stands

is obtained by compounds of the formula XR -C- COR ¹

CN in which

R is as defined under 1, R is hydrogen or Si (CH)

14 R has the meaning given above has reacted with inorganic acids.

4. It has also been found that the compounds of formula XI

OH R ¹ -C CO-R ¹⁴ XI

CONHCOR

in which R has the meaning given under 1, R * has the meaning given under 3 and

Le A 22 012

λ *.

~ 24 -

R is hydrogen, optionally substituted alkyl, alkenyl, cycloalkenyl or aryl

gets

by giving compounds of the formula X.

r ¹ - ^^ -. COR ¹⁴

in which

1 14 R, R have the abovementioned meaning and R ^{15 is} hydrogen or Si (CH ₃ J ₃ , with acids of the formula XII

R ¹⁶ -COOH XII

in which

R has the meaning given above or its anhydrides

Le A 22 012

in the presence of inorganic acids.

5. It has also been found that the compounds of formula XIII

CONH ₂ XIII CONHR ¹⁷

in which

R is as defined under 1, R is alkyl, cycloalkyl, alkenyl, amino, alkylamino, arylamino, acylamino, dialkylamino, alkylarylamino

obtained by reacting compounds of formula XIV

• OH

CONH ₂ XIV COOR ¹⁸

in which

R has the meaning given above and

1 p

R is alkyl or cycloalkyl,

Le A 22 012

with compounds of the formula XV

R ¹⁷ NH ₂ XV

in which

R has the meaning given above.

6. It has also been found that the compounds of the formula XVI

-OH

R ¹ -CONHR ¹⁷ XVI

CONHR

in which

R and R have the meaning given under 5, by reacting compounds of the formula XVII

, 0H COOR ^1!

r ^x _C -COOR XVII

in which

Le Ά 22 012

β Ο » ^J O

R has the meaning given above and

18 R are the same or different and are alkyl or

Are cycloalkyl,

with compounds of the formula XV

R ¹⁷ NH ₂ XV

in which

R has the meaning given above, implemented.

7. It has also been found that the compounds of the formula XVIII

R ¹ -CONH ₂ XVIII

'COO Met

in which

R has the meaning given under 1.

Met is one equivalent of an alkali or alkaline earth,

Le A 22 012

obtained by reacting compounds of formula XIV

OH

CONH ₂ XIV

in which

1 18 R, R have the meaning given under 5. with compounds of formula XIX

Met-OH XIX

in which Met · has the meaning given above.

8. It has also been found that compounds of formula XX

^ OH

R ¹ -CCOO Met XX

• COO Met

in which

La A 22 012

R and Met have the meaning given under 7

obtained by reacting compounds of formula XVII

OH

OI .18

R ¹ -C COOR ¹⁸ XVII

'COOR

in which

118 R, R are those given under 6. (above)

Meanings have with compounds of formula XIX MetOH in which

Met the meaning given in 7.

Has

implements.

9. It has also been found that compounds of formula XXI

Le A 22 012

-0-R ¹⁹

_R ¹ _ _Cr CONH-R ²⁰ XXI

-CONH-R ²¹

in which

R the above under l. indicated meaning

has

19 R for alkylcarbonyl or arylcarbonyl,

stands,

20 R for forrayl, alkylcarbonyl, alkenyl

carbonyl, cycloalkenylcarbonyl or arylcarbonyl,

R ²¹ for hydrogen, forrayl, alkylcar

is carbonyl or arylcarbonyl,

receives ·

by reacting compounds of the formula XXII

_ ^ 0-R ¹⁹

R ¹ -CCN XXII

CN

in which

19 '

R and R have the abovementioned meaning,

with acids of the formula XXIII

Le A 22 012

R ²⁰ -OH XXIII

in which

R has the meaning given above

or their anhydrides in the presence of inorganic mineral acids, optionally with the addition of water.

10. It has also been found that compounds of formula XXIV

R ³ -C-CONH ₂ XXIV

CONH-R ²⁰

in which

R has the meaning given under 1 and

20

R is formyl, alkylcarbonyl, alkenylcarbonyl,

Cycloalkenylcarbcnyl, arylcarbonyl is obtained by reacting compounds of formula XXV

^ _ ^ O-Si (CH ₃ ) ₃

R-C - CN XXV

in which

Le A 22 012

R has the meaning given above, with acids of the formula XXIII

20 R-OH XXIII

in which

20 R has the meaning given above

or their anhydrides in the presence of inorganic mineral acids.

11. It has also been found that compounds of formula XXVI

OR ¹⁹

R ² -Cf ^ -CO-NR ²² R ²³ XXVI

CO-NR ²⁴ R ²⁵

in which 1

R, R have the meaning given under 9,

R is alkylcarbonyl,

24 R is hydrogen or alkylcarbonyl, 23

R is hydrogen or alkyl, R is hydrogen or alkyl,

Le A 22

ο o

gets

by reacting compounds of the formula XXVII

R-C

CONHR • CONHR

19a 23

XXVII

25

in which

25

1? 3 25

R, R '", · R have the abovementioned meaning,

ISa

is hydrogen, alkylcarbonyl, arylcarbonyl

with acid anhydrides of the general formula XXVIII

² I

XXVIII

in which

has the meaning given above

implements.

Le Ά 22 012

12. It has also been found that compounds of formula XXIX

R ³ -C-CONHR ²² XXIX

COR ²⁶

in which

1 19 22

R, R, R have the meaning given under 11

2 6

R is alkoxy or dialkylamino,

gets

by giving compounds of the formula XXX

OR ^19a

r ¹ -c conh ₂ xxx

: or ²⁶

in which

1 19a

R, R is the meaning given under 11

to have,

2 6

R has the meaning given above,

Le A 22 012

with acid anhydrides of the general formula XXVIII

R ²²

^ O XXVIII

Ε ²² '

in which

22 R has the meaning given above

implements.

13. It has also been found that the compounds of formula XXXI

OH

R ³ -C r -CONH ₂ XXXI

CO-NH-NH-R ²⁷

in which

R has the meaning given under 1

27

R is alkylaminocarbonyl, alkylaminothiocarbonyl, arylaminocarbonyl, arylaminothiocarbonyl, alkylsulfonylaminocarbonyl, arylsulfonylaminocarbonyl, alkylcarbonylaminocarbonyl, arylcarbonylaminocarbonyl and the like

corresponding thiocarbonyls,

gets

Le A 22 012

by giving compounds of the formula XXXII

OH

CONH ₂ CONHNH,

XXXII

in which R has the meaning given above with iso (thio) cyanates of the formula XXXIII

N ⁰ NCO (S)

XXXIII

in which

R ^{28 is} alkyl, aryl, alkylsulfonyl, aryl

sulfonyl, alkylcarbonyl, arylcarbonyl

implements.

14. It has also been found that the compounds of formula XXXIV

OH

"CONH ₂ CONH-NH-R

29

XXXIV

in which

Le A 22 012

9 β

R has the meaning given under 1

29

R is alkylcarbonyl, arylcarbonyl, alkylsulfonyl,

Arylsulfonyl is obtained by reacting compounds of formula XXXII

OH

- ¹ "CONH ₂ XXXII

CONHNH ₂

in which

R has the meaning given above

with acylating agents of the formula XXXV R ²⁹ -A XXXV

in which

29

R has the meaning given above

A is halogen, CN, C,, -alkylcarbonyloxy, aryl · carbonyloxy

implements.

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* ο ν ^: ^;; - ^J '"e ⁹ ""' S ·; <3 -n ' C ο β«

15. It has also been found that the compounds of formula XXXVI

• OH CONH ₂

CONHN = C '

XXXVI

in which

IQ Q O τι "^

have the meaning given under 1

gets

by giving compounds of the formula XXXII

OH CONH ₂

CONHNH2

in which R ¹

XXXII

has the meaning given above

with carbonyl compounds of formula XXXVII

C = O

XXXVII

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in which

8 9

R and R have the meaning given above.

16. It has also been found that the compounds of formula XXXVIII

• OH

R ¹ -C CONHNR ³⁰ R ³¹ XXXVIII

CONHNR ³⁰ R ³¹

in which

R is as defined under 1, R is hydrogen,

r> ι 2 8 2 9

R ^J for those at R and R under procedures

13 and 14 (above) meanings or

R ⁸

30 31 - ""

R and R together for the rest = C

8 9 where R and R are as defined under 1

has stood,

obtained by reacting the compounds of formula XXXIX

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OH

1 - '"R

-C - ^ = T (CONHNH ₂ \ XXXIX

with compounds of the formulas XXXIII, XXXV or XXXVIi

Op OQ

R NCO (S) XXXIII; R-A XXXV; "£

C = O XXXVII R ⁹ in which

2 8 2 9 8 9

A, R, R, R, R have the meanings given under 13, 14, 15

implements.

17. It has also been found that the compounds of formula XL

R ¹ -c'-CO-N XL

CO-R ³⁵ in which

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R has the meaning given under 1

R ^{32 is} trialkylsilyl, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, alkylcarbonyl, arylcarboxynyl

R ^{33 is} hydrogen or alkyl, R ^{34 is} trialkylsilyl,

R ^{J is} alkoxy, cycloalkoxy, trialkylsilylamino, trialkylsilylalkylamino, dialkylamino, nitrogen-containing saturated heterocycles which optionally contain further heteroatoms,

where these radicals may optionally be substituted stands

gets

by giving compounds of formula XLI

OR ³⁶

R ¹ -C_ CONHR ³³ XLI

COR ³⁷

in which

1 33 R and R have the abovementioned meaning and

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R is hydrogen, alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, alkylcarbonyl, arylcarbonyl

.37

for alkoxy, cycloalkoxy, amino, alkylamino, dialkylamino, nitrogen-containing saturated heterocycles which optionally contain further heteroatoms, where these radicals may optionally be substituted,

with trialkylsilyl compounds of the formula VIII

Alkyl of

Alkyl Si-W

VIII

in which

W has the meaning given under 2b

implements.

18. It has also been found that the compounds of formula XLV

OH CONHR

38

CONHR

XLV

in which

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R has the meaning given above under 1

3 8 R is tert-alkyl having 4-18 C atoms, is obtained by reacting compounds of formula XXV

^^ OSi (CH ₃ ) ₃

R -C CN XXV

^^ "" ^ • CN

in which

R has the meaning given above

a) with a tertiary alcohol of the general formula XLVI

R ^{3 8} -0H XLVI

in which

3 8 R has the meaning given above,

in the presence of acids or b) with an alkene of the general formula XLVII R ³ I .R ⁴⁰

C = C XLVII

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in which

3 9 'R are the same or different and for

Hydrogen, alkyl stand

40 R are the same or different and are alkyl

stand

in the presence of acids,

19. It has also been found that the compounds of formula XLVIII

OR ¹⁹

CONHR ³⁸ XLVIII CONH

in which

R is the meaning given under 1 has 3 8

R has the meaning given in 18,

19

R is alkylcarbonyl or arylcarbonyl

obtained by reacting compounds of formula XXII

_R ¹ -C-CN XXII

• CN

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in which

1 19 R and R have the abovementioned meaning

a) with a tertiary alcohol of the general formula XLVI

"5 ρ

R-OH XLVI

in which

3 8 R has the meaning given above

in the presence of acids or

b) with an alkene of formula XLVII

R ³ IR ⁴⁰

^ .C = C XLVII

R ⁴⁰

in which

39

R and R have the meaning given under 18

in the presence of acids.

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- 46 20. Compounds of formula II

OH

1 ---- _R ^x _ _c CO-R II

CO-R ⁴

in which

13 4 R, R, R have the meaning given under 1

are new and are prepared by the methods 3, 4, 5, 6, 7, 8, 13, 14, 15, 16.

21. The compounds of the formula X.

1 - "" ^ R-C COR X

CN

in which

R, R, R have the meaning given under 3 and 4,

are prepared by reacting compounds of formula XLII

R ¹ -C = O

¹ XLII

COR ¹⁴

in which

1 14 R and R are as defined above

to have

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with HCN or HCN-releasing compounds or with trimethylsilyl cyanide.

22. The compounds of the formula X.

^ 0-R ¹⁵

R ¹ -C COR ¹⁴ X

in which

R has the meaning given under 1,

R is hydrogen or trimethylsilyl,

14 R for amino, alkylamino, arylamino, dialkylamino, cycloalkylamino, alkenylamino, nitrogen-bonded nitrogen-containing ge

saturated heterocyclic radicals which optionally contain further heteroatoms, where these radicals may optionally be further substituted,

are new.

23. The compounds of the formula XVII

• OH COOR ¹⁸ XVII

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in which

1 18 R, R the meaning given under 6 and 8

to have

are obtained by using compounds of formula XXV

^^ OSi (CH ₃ J ₃

R ¹ -CCN XXV

 CN

in which

R has the meaning given under 1 with alcohols of the formulas XLIII

1 S R-OH XLIII

in which

18 R has the meaning given above in the presence of inorganic mineral acids

 24. Compounds of the formula XXII

0-R ¹⁹

"CN CN

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η o

in which

1 19 R and R are as defined under 9 meaning

to have

are known or can be prepared by known methods. (Journal of Chemistry, Vol. 27 39, p.260 (1889); Chemistry a. Industry 1970, p. 1408).

25. Compounds of the formula XLIV

OH

1 - "" ^ RC CONH ₂ XLIV

CONH.

in which

R has the meaning given under 1

are prepared by reacting compounds of formula XXV

^^^. OSi (CH ₃ )

r ¹ _C - CN XXV

CN in which

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R ^{x has} the meaning given above saponified with inorganic acids. 26. Compounds of the formula XXV

^^ OSi (CH ₃₎ R ³ -C CN XXV

CN

in which R have the meaning given under 1

are known or can be prepared by known methods (Chem. Ber 106 , page 87 (1977); Tetrahedron Letters No. 17, 1449-1450 (1973); DE-OS 3,140,632).

7. Compounds of the formula XLII

R ¹ -C = O

COR ^{14 XLI1}

in which

1 14 R and R have the meaning given under 21

are known in part. They are prepared in a manner known per se (Tetrahedron Letters

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1980, 3539; Annalen der Chemie / 10 /, _9, 241; DE-OS 2 249 820 and DE-OS 2 708 * 189).

In the following, the implementation of the method mentioned under 2-25 "(above) is described in more detail:

Procedure 2a ..

The reaction of the compounds of the formulas II and III is optionally carried out in the presence of acid acceptors, if appropriate in the presence of a catalyst, if appropriate in the presence of a diluent. The course of the reaction may e.g. represented by the following formula scheme:

S2H

The compounds of formulas II and III are used in equimolar amounts, an excess of one or the other component brings no significant advantages.

Preferred compounds of the formula II are those

3 4 those used in the substituents R, R have the preferred meanings mentioned in the compounds of formula I. Some of the compounds of the formula II are the subject of an earlier application of the Applicant which does not belong to the prior art (German Application P 31 40 275.5). They go to the there

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produce specified method. They can also be prepared by the processes described below (Processes 3, 5, 6, 20, 7, 10, 13, 14, 15, 16, 24. The following compounds of the formula II may be mentioned in particular:

Phenylhydroxyuronic acid diamide, 2-, 3-, 4-chlorophenylhydroxy-nialonic acid radical, 2, 3-dichlorophenylhydroxymalonic acid diamide, 3,4-dichlorophenylhydroxy-malonic acid diuretic acid, 3, S-dichlorophenylhydro-nalonic acid diamide, 2, 4-Dichloro-phenyl-hydroxy-malonic acid diamide, 2,5-dichlorophenyl-hydroxy-4-vinyl-dianide, 2,6-dichlorophenyl-hydroxy-ammonium diurea, 2, 3,. 4-Nitrophenylhydroxy-nonic acid diamide, 2-chloronoethylphenyl-hydroxynalonic acid diolide, 2-, 3-, 4-trifluoromethylphenyl-hydroxynalonic acid diamide, 2-, 3-, 4-methoxyphenylhydro-natraleic acid diamide, 2,6-dimethoxyphenyl-hydroxy-malonic acid disulfide , 2-, 3-, 4-tolyl-hydroxy- ~ alor, 3äurediamid, 2-, 3-, 4-Trif luoririethcxyphenyl-hydroxy-rr.alonsäurediamid, 2-, 3-, and 4-fluorophenyl-hydroxynalon3äuradia; nid _/ 3,4-dichlorophenyl-hydroxy-raalonsäureamid-methylamide, phenylhydroxy-malonic acid-diethylanid-arnid, Cyclohexylhydroxyraalonsäure-iuethyles ter-anid, 3, 4-dichlorohenyl-hydroxyrr.alonsäure-dimethyl ester, 3-chlorophenyl-hydroxy-ralalonsäura-diethylester, 3 , 4,5-trichlorophenyl-hydroxy-5-malon acid ethyl ester-amide, 4-chlorophenyl-hydroxy-malonsäureisopropylesteranid, 3, 5-Dichlorpher.yl-hydroxy-malonsäureaaid -.?. 'orphol anid iny 1, 3, 5 Dichloro-4-llydroxyphenyl, 3,5- dichloro-4-aninophenyl, 3,5-dichloro-4-methoxyphenyl, 3 -chloro-4-hydrocyanyl-hydroxyurialic acid diamide or di- ethyl ester, 3,4-dichlorophenyl-hydroxy-naphthalene

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acid-bis-isopentylaraid, phenylhydroxy-malonic acid bismethylamide, cyclohexy-hydroxy-malonic acid diamide, 2,3,4-; 2,3,6; 3,4, S-trichlorophenyl-hydroxy-malonic acid diamide, 2,3,4,5-; 2,3,5,6-tetrachlorophenyl-hydroxy-malonic acid diamide, pentachlorophenyl-hydroxy-malonic acid diamide.

As examples of the starting materials of the formula (III) may be mentioned:

Methyl bromide, methyl iodide, ethyl bromide, ethyl iodide, 1-iodopropane, 2-iodopropane, allyl chloride, allyl bromide, propargylbroidide, benzyl chloride, benzyl bromide, dimethyl sulfate, diethyl sulfate.

Suitable diluents are all inert organic solvents, these include in particular aliphatic and aromatic, optionally halogenated hydrocarbons, such as pentane, hexane, heptane, cyclohexane, petroleum ether, gasoline, ligroin, benzene, toluene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, chlorobenzene and O-dichlorobenzene, further ethers such as diethyl and Dibtuylether, glycol dimethyl ether and Diglykoldimethyleter, tetrahydrofuran and dioxane, further ketones such as acetone, methyl ethyl, methyl isopropyl and methyl isobutyl ketone, as well as esters such as ethyl acetate and methyl ester, further nitriles , such as Acetonitrile and propionitrile, benzonitrile, glutaronitrile, moreover amides, e.g. Dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and dimethyl sulfoxide, tetramethylene sulfone and hexamethylphosphoric triamide.

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Acid acceptors which can be used are all customary acid binders. These include preferably alkali metal carbonates, hydroxides or alcoholates, such as sodium or potassium carbonate, sodium and potassium hydroxide, sodium and potassium methylate or ethylate, furthermore aliphatic, aromatic or heterocyclic amines, for example trimethylamine, triethylamine, tributylamine, dimethylaniline, dimethylbenzylamine and pyridine.

As catalysts it is possible to use compounds which usually serve in reactions in two-phase systems of water and water-immiscible organic solvents for the phase transfer of reactants (phase transfer catalysts). As such, especially tetraalkyl and Trialkylaralkyl-ammonium salts with pre-T5 preferably 1 to 10, preferably 1 to 8 carbons per alkyl group, preferably phenyl as Arylbestandteil the aralkyl group and preferably 1 to 4, in particular 1 or 2 carbon atoms in the alkyl moiety of the aralkyl groups preferred , In this case, especially the halides, such as chlorides, bromides and iodides, preferably the chlorides and bromides in question. Examples which may be mentioned are tetrabutylammonium bromide, benzyltriethylammonium chloride and methyltrioctylammonium chloride.

The reaction temperature is maintained between about O ⁰ C and 13O ⁰ C, preferably between about 20 ⁰ C and 60 ⁰ C. The process is preferably carried out at atmospheric pressure.

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The isolation of the end products takes place in a generally customary manner.

Method 2a

The reaction of the compounds of the formulas II and IV is optionally carried out in the presence of acid acceptors, if appropriate in the presence of a catalyst, if appropriate in the presence of a diluent.

The course of the reaction may e.g. represented by the following formula scheme:

Cl

Cl

Cl

! -CONE-

\ ^l

CONH ₂

CONH ₂

Here too, preference should be given to processes 2a. mentioned compounds of formula II mentioned.

Preferred compounds of the formula IV are:

Benzoyl chloride, 3,4-dichlorobenzoyl chloride, 3-chlorobenzoyl bromide, acetyl chloride, acetic anhydride, propionyl chloride, benzoyl cyanide, ethyl chloroformate, methyl chloroformate, methylsulfamoyl chloride, dimethylcarbamoyl chloride, phenyl chloroformate.

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The process can be carried out either in the presence of an acid acceptor or without base. If the reaction is carried out in the presence of an acid acceptor, the compounds of the formulas II and IV are employed in equimolar ratios; a slight excess of one or the other component brings no significant advantages.

Suitable diluents are those mentioned in method 2a .. in question.

Suitable acid acceptors are those mentioned in process 2a. Some of these acid acceptors act as catalysts. Other catalysts are mentioned in process 2a.

The acid acceptor is preferably used at least equimolar with respect to the compound IV. It may also be used in excess to serve as a diluent.

Some acid acceptors, preferably the tert. Amines e.g. Triethylamine, pyridine, can be added in small amounts as catalysts and favorably influence the reaction.

The process is preferably carried out from 0 to 130 ⁰ C between 10 and 60 ° C. It is preferable to operate at normal pressure. The isolation of the end products takes place in a generally customary manner.

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According to the procedure described above for process 2a ", a reaction of the compounds of formula II is achieved only at the hydroxyl group.

Another procedure for method 2a "is that the compound of formulas II and IV are heated without the presence of acid acceptors, optionally in the presence of diluents and or catalysts.

In this case, the compounds of the formula IV are used in at least an equimolar amount, preferably in excess (1.1-10 times, preferably 1.2-5 times, in particular 1.3 times).

The diluents are the same as described under 2a.

The reaction is performed between 0 and 5 2 00 ⁰ C and 15O ⁰ 70 preferably zwisehen C. It is preferable to operate at normal pressure.

The catalysts used in process 2a. mentioned question. The compounds H-Z (e.g., HCl, HCN) released in this procedure are removed during the reaction.

After the procedure described so far, a reaction of the compounds of formula II is achieved at the hydroxyl group.

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If acid anhydrides are used as compounds of the formula IV, the reaction of the compounds of the formula IV is usually carried out both at the hydroxyl group and, if possible, at the amide group (cf., Process 11).

However, under certain conditions, the reaction with the acid anhydrides may be limited to the reaction of the hydroxyl group of the compounds of formula II.

This requires that compound II and acid anhydride be used only in approximately equimolar ratio.

In general, the reaction is carried out with acid anhydrides as described above. As catalysts, however, are also acids such as mineral acids such as HCl, H ₃ SO ₄ , H ₃ PO ₄ , HCiO ₄ or strong organic acids such as p-toluenesulfonic acid or trifluoromethanesulfonic acid, use. Likewise, Lewis acids such as AlCl ₃ , BF ₃ , ZnCl, FeCl ₃ can be used for this purpose.

Method 2a ₃

The reaction of the compounds of the formula II and V is optionally carried out in the presence of a catalyst, if appropriate in the presence of a diluent.

The reaction sequence can be represented by the following formula scheme_

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OH _{/ ==} ^ ^ 0-CONHCH ₃

σ XV-C-CONH ₂ + OCN-CH ₃ ><(Λ-C-CONH ₂

CONH ₂ CONH ₂

Preferably, the compounds of the formula II listed in process 2a may also be mentioned here.

Preferred compounds of the formula V are: isocyanates which are derived from the following amines:

Methylamine, ethylamine, propylamine, isopropylairin, butylamine, iso-butylamine, tert-butylamine, hexylamine, dodecylamine, 2-ethylhexylamine, tetradecylamine, hexadecylamine, octadecylamine, allylamine, 2-methoxyethylamine, 2-ethoxypropylamine, 3-butoxypropylamine, 3-aminopropanoic acid 2-methylpropyl ester, 6-aminohexanitrile, lysine ester, 1,1-aninoundecanoic acid ester, cyclohexylamine, trimethylcyclohexylamine, 2-borbornylmethylamine, aniline, o, m, p-chloroaniline, 2,3-, 2,4-, 2,5-, 2,6-dichloroaniline, 3,4-, 3,5-dichloroaniline, p-nitroaniline, m, o, p-tolylamine, 3-trifluoromethylaniline, 3-chloro-4-methylaniline, 4-chloro-3-methylaniline, benzylamine , Phenylcyclohexylamine, naphthylamine.

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Further isocyanates such as e.g. 2-Ethyl-hexyl-oxy-carbonyl isocyanate, tosyl isocyanate, 3,4-, 3,5-dichloro-benzoyl isocyanate, 4-chloro-benzoyl isocyanate, 3-chloro-benzoyl isocyanate, 2, β-dichloro-benzoyl isocyanate, isopropionyl isocyanate, cyclohexylcarbonyl isocyanate.

These isocyanates are known compounds. They can be prepared by methods known per se.

Diluents are those used in process 2a. mentioned question.

Suitable catalysts are the catalysts customary in reactions with isocyanates. As such may be mentioned; tert. Amines such as triethylamine, N-methylmorpholine, 1,4-diazabicyclo- (2,2,2) -octane (DABCO) β, β'-dimethylaminodiethyl ether, dimethylbenzylamine, metal1-catalysts of Zn, Sn, Pb such as dibutyltin dilaurate, dibutyltin oxide , Tin octoate, lead octoate, zinc octoate, zinc chloride, zinc acetate.

The reaction is carried out 'between 5 0 and 15 0 ⁰ C preferably between 60 - 110 ⁰ C performed. It is preferably carried out under atmospheric pressure.

The compounds of formulas II and V are used in equimolar amounts, a slight excess of one or the other component brings no significant advantages.

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The final products are isolated in a generally conventional manner.

Method 2a.

The reaction of the compounds of the formula II with compounds of the formula VI and then with compounds of the formula VII is optionally carried out in the presence of diluents, if appropriate in the presence of a catalyst, if appropriate in the presence of acid acceptors.

The course of the reaction may e.g. in the case of reaction with amines, be represented by the following formula scheme:

/ Ά nw 0 O-CONH-CO-NH-

1) C-CONH ₂ + (T) OCT-C-Hal> C-CONH ₂

^N C0NH ₂ φ / V ^X _conh

The process is carried out in two stages.

The course of the reaction may e.g. in the case of reaction with water, given by the formula scheme below:

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T) OCN-COHaI

OCONH- / 2

-CONH ₀ ·

\ ²

CONH ₂

The process is carried out in two stages. Suitable diluents for both process variants are those mentioned under process 2a.

In general, no catalysts are needed for the 1, stage. However, it can be worked with the aid of the catalysts mentioned under 2a.

The reactions are at 0 - preferably carried out at 20 4O ⁰ C 70 ⁰ C.

Method 2b

For example, if phenylhydroxymalonic acid diamide and trimethylsilyl cyanide are used as starting materials for process 2b, the reaction can be sketched by the following formula:

OH J

+ (CH ₃ ) ₃ SiCN

. HCN

0Si (CH ₃ ) ₃

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The hydroxy-malonic acid compounds to be used as starting materials are defined by the formula (II). The compounds of the formula II listed in process 2a.

The trialkylsilyl derivatives of the formula VIII are known. Alkyl in the general formula is preferably identical or different C.sub.-alkyl radicals, such as methyl, ethyl. The substituent W preferably stands for the radicals halogen, such as chlorine, and also CN.

Specifically, may be mentioned:

Trimethylsilyl chloride, trimethylsilyl bromide, trimethylsilyl iodide, trimethylsilyl cyanide, tert-butyldimethylsilyl chloride or cyanide.

Suitable diluents are those mentioned in method 2a .. in question.

As acid acceptors and catalysts are those in process 2a. mentioned question.

The reaction temperature is between about 0 ⁰ C and 13O ⁰ C, preferably between about 20 ⁰ C and HO ⁰ C. The process is preferably carried out at atmospheric pressure.

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For carrying out the process (2b) according to the invention, the compounds of the formula (II) and the trialkylsilyl compounds are usually employed in equivalent amounts.

The isolation of the end products takes place in a generally customary manner.

Method 3

If trimethylsilyloxy-phenylmalononitrile monomethyl ester is used as starting material and 96% sulfuric acid as saponification agent, the course of the reaction can be represented by the following formula scheme:

OSi (CH ₃ )

 CN

_so

Some of the compounds of the formula X are known or can be prepared analogously to known processes {Jap. Note 3034 - 729). Their preparation is described in more detail under Method 21 (below).

Specifically, the following compounds may be mentioned:

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0-R

15

R ¹ -CίCOR ¹⁴

CN

.14

15

Cl C

-OCH

Si (CH ₃ )

ÜD-

NH,

-N (CH _3. )

Si (CH ₃ ) ₃

Si (CH ₃ ) ₃

G-

NH

-N 0

Si (CH ₃ ) ₃

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The diluent used in the saponification is generally water. The saponification can be carried out in anhydrous or water-containing acids, frequently even small amounts of water are sufficient to obtain the desired end products.

The amount of water can, however, in a wider range between 2% and 75% based on the amount of acid used, can be varied. It is also possible to first dissolve the starting materials of the formula X in an anhydrous acid and to add the required amount of water at a later time.

Suitable acids which may be mentioned are preferably: sulfuric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid, boric acid, perchloric acid. Particularly preferred are sulfuric acid (H ₂ SO ₄ ) and hydrochloric acid (HCl).

In some cases, the end products of general formula IX are slightly soluble in water and must therefore be removed therefrom by means of an extractant. Suitable extractants are all inert organic solvents which do not mix with water, or only slightly, into consideration. These include toluene, xylene, chlorobenzene, dichlorobenzene, ethyl acetate, methylene chloride, chloroform, carbon tetrachloride and ethers. In general, however, an extractant is not necessary.

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The reaction temperatures can be varied within a substantial range. In general, one works between about -15 ⁰ C to 100 ⁰ C, preferably between 0 and 8 0 ⁰ C, in particular between 20 and 60 ⁰ C.

The reaction is normally at atmospheric pressure. But it can also be done at elevated pressure. In general, one works at pressures between about bar and about 10 bar, preferably between 1 bar and 5 bar.

In carrying out one uses for 1 mole of the compound of formula X about 0.5 to 2 0 mol, preferably 1 to 5 moles of inorganic acid.

The compounds of formula X dissolved in the acid are poured onto ice 5 after stirring for 30 minutes to two hours and recovered either by suction or extraction. The purification is generally carried out by recrystallization.

Method 4

The reaction of the compounds of the formula X with acids of the formula XII or their anhydrides in the presence of inorganic acids is optionally carried out in the presence of diluents.

The course of the reaction may e.g. represented by the following formula scheme:

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CH ₃ COOH H ₂ SO ₄

C-COOC ₉ HC \

CONHCOCH.

Preferably, the compounds of the formula X listed in process 3 are also mentioned here:

As inorganic acids, the acids listed in process 3 are also preferably mentioned here.

Preferred as organic acids of the formula XII are:

Formic, acetic, propionic, butyric, isobutane, valerian, capron, heptyl, caprylic, capric, lauryl, stearic, benzoic, phenylacetic, toluene, naphthoic, mono- , Di- and trifluoro- or -chloroacetic acid, acrylic acid, methacrylic acid, 2-cyclohexenecarboxylic acid.

The process is conducted at temperatures from 0 - 100 ⁰ C, preferably 20 - 6O ⁰ C and preferably carried out under normal pressure.

The process is preferably carried out without a diluent.

The order of addition of the reaction components is arbitrary. Preference is given to the compound of the formula

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IX added to a mixture of the organic acid and the inorganic mineral acid.

The work-up is carried out in the usual way. Method 5

The reaction of the compounds of the formula XIV with compounds of the formula XV is carried out, if appropriate, in the presence of a diluent.

The course of the reaction may e.g. represented by the following formula scheme:

OH ^0H



O ^C ^ ^C0NH 2 + 0 ^ 2 - * (]> cl CONH ₂

COOCH ₃

CONH

₃ \

CO- / \

The compounds of formula XIV are new. They are prepared by the process indicated under process 3 (above).

Preferably be mentioned in detail:

OH

1 R-C

COOR ¹⁸

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18

OCH.

OC ₃ H ₇ X OC ₂ H ₅

Dia compounds of the formula XV are known. In the following, preference may be given to: methylamine, ethylamine, propylamine, isopropylamine, butylamine, hexylamine, cyclohexylamine, neopentylamine, isopentylamine, ethanolamine, hydrazine, phenylhydrazine, acetylhydrazine.

The compounds XIV and XV are reacted in an equimolar ratio. An excess of compounds of formula XV may be advantageous.

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Suitable diluents are those mentioned in process 2a ₁ . Additionally and particularly suitable are also alcohols such as methanol, ethanol, isopropanol.

The process is carried out at 20 - 100 ⁰ C and carried out preferably at atmospheric pressure - 120 ⁰ C., preferably at 50th

The work-up is carried out in the usual way. Procedure β

The reaction of the compounds of the formula XVII with compounds of the formula XV is optionally carried out in the presence of a diluent.

The course of the reaction may e.g. represented by the following formula scheme:

OH ^ OH

COOCH ₃ + CH ₃ NH ₂ > \ j) ~ C - CONHCH ₃

COOCH ₃ CONHCH ₃

The compounds of the formula XVII are new. They are prepared according to the procedure given under Method 23 (below).

The following compounds may be mentioned by preference:

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Phenylhydroxymalonic acid diethyl, 3,4-, 3,5-Dichlorphenylhydroxymalonsäuredimethylester, 4-Chlorphenylhydroxymalonsäurediethylester.

As compounds of the formula XV, those mentioned in process 5 (above) are preferably used.

Compounds of the formula XVII and XV are used in a molar ratio of 1: 2. An excess of compound of formula XV may be advantageous.

The reaction is carried out as described in method 5 (above).

Method 7

The reaction of compounds of form XIV with compounds of formula XIX is carried out in the presence of dilution solvent.

The course of the reaction may e.g. the following equation scheme are reproduced:

j , OH / = \ ^0H

Cl- {/ V ^G -CONH, Cl- / C-CONH-

COOCH-. COONa

The compounds of formula XIV are new. They are prepared by the method given in Method 3 (above). Preferred are those mentioned in process 5 (above).

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Preferred compounds of the formula XIX are alkali metal or alkaline earth metal hydroxides such as NaOH, KOH, Ca (OH).

The compounds XIV and XIX are reacted in the stoichiometric ratio.

The process is of 10 - carried out 4O ⁰ C - 80 ⁰ C., preferably at 20th

Preferred diluents are water, alcohols such as methanol, ethanol, isopropanol and mixtures thereof with one another and with water. The process can also be carried out in the two-phase system of water and a water-immiscible organic diluent. Preference is then given to working in the presence of the above-mentioned phase transfer catalysts.

The workup is carried out by conventional removal of the diluent.

Method 8

The reaction of the compounds of the formula XVII with compounds of the formula XIX is carried out in the presence of diluents.

The course of the reaction may e.g. represented by the following formula scheme:

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OH

KQH ν

OH C - COOK

COOK

COO-C ₂ H ₅

The compounds of the formula XVII are new. They are prepared by the method given under Method 2 3 (below).

Specifically, the compounds mentioned in Process 6 (above) may be mentioned as being preferred.

The procedure is carried out as described in Method 7 (above).

Method 9

The reaction of the compounds of the formula XXII with acids of the formula XXIII or their anhydrides is optionally carried out in the presence of diluents.

The course of the reaction may e.g. be represented by the following reaction scheme:

O-C

CN

CH ₃ COOH

H ₂ SO ₄

- CONHCOCH.

N.

CONHCOCH.

Compounds of formula XXII are known in part. They can be prepared by known methods.

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ο ο ~>' ο

(Journal of Practical Chemistry / 2/39, p.260 (1889); Chemistry a., Industry, 197C, p. 1408).

Specifically, may be mentioned:

OR

• CN CN

19

5 R ^J

Cl

As inorganic mineral acids, the acids listed in process 3 are preferably mentioned.

The acids mentioned under process 4 (above) are preferably mentioned as organic acids of the formula XXIII.

The process is carried out as described in process 4 (above).

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Method 10

The reaction of the compounds of the formula XXV with acids of the formula XXIII or their anhydrides is optionally carried out in the presence of diluents.

The course of the reaction may e.g. represented by the following formula scheme:

CH ^ COOH j ^

H SO, CONHCOCH ₃

The compounds of formula XXV are known in part. They can also be prepared by methods known per se (Chem. Berichte 106 , 587 (1973); Tetrahedron Letters No 17, 1449-1450 (1973)). Preferred are:

o-, m-, p-chlorophenyl, 2,3-dichlorophenyl, 3,4-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, o, m -, p-nitrophenyl, o-chloromethylphenyl, o-, m-, p-methoxyphenyl, 2,6-dimethoxyphenyl, o-, m-, p-tolyl, o-, m-, p-trifluoromethoxyphenyl -, o-, m-, p-fluorophenyl, cyclohexyl, -trimethylsilyloximalonsäurenitril.

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As inorganic mineral acids, the acids listed in process 3 are preferably mentioned.

Preferred organic acids of the formula XXIII are the acids listed under process 4 (above).

The procedure is carried out as described in Method 4 (above).

Method 11

The reaction of the compounds of the formula XXVII with acid anhydrides of the formula XXVIII is optionally carried out in the presence of diluents, if appropriate in the presence of catalysts.

The course of the reaction may e.g. represented by the following formula scheme:

ClH \ / Γ C-CONH ₂ + Λ. - Λ . «W /

⁰ ^ CH ₃ -CO-

The compounds of formula XXVII are new. They are partly the subject of an application of the Applicant that is not yet part of the prior art (German Application P 31 40 275.5).

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You can according to the under 2a and 2a. can be obtained.

The compounds listed under 2a_ are preferably mentioned. In addition, the O-benzoyl, O-acetyl, 0-0-3,4-dichlorobenzoyl, O-4-chlorobenzoyl, O-3-chlorobenzoyl, O-propionyl derivatives of the Hydroxyraalonsäureamide listed there may be mentioned, as well as the corresponding hydroxymalonic acid amide and Hydroxymalonsäurebis-methyl amides.

Acid anhydrides of the formula XXVIII are known. Preference is given to acetic anhydride, propionic anhydride.

The reaction is carried out by reacting at least the stoichiometric amount of anhydride with compound XXVII. In this case, the reaction of the hydroxyl group and in addition to one or both amide groups in dependence on the added amount of anhydride and the reaction time.

Suitable diluents are those mentioned in process 2a_.

The process is preferably carried out in the presence of the anhydride used as diluent.

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As catalysts are mineral acids such as HCl, H SO., H ₃ PO ₄ , HClO ₄ in question. The catalyst is added in 0.01-10% of the reaction mixture,

The process is carried out at 20 - 12O ⁰ C preferably 40 - 90 ⁰ C.

The work-up is carried out in the usual way. Method 12

The process conditions of process 12 are identical to those of process 11. The starting compounds of formula XXX are novel. They are obtained by the processes listed under 2a_ and 2a ₁ . Preferably, the preferred starting compounds listed for the process 2a are also mentioned here.

Method 13

The reaction of the compounds of the formula XXXII with the isocyanates of the formula XXXIII is optionally carried out in the presence of diluents, if appropriate in the presence of catalysts.

The course of the reaction may e.g. represented by the following formula scheme:

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The compounds of formula XXXII are new. They are prepared according to the method described under 5. The compounds of the formula XXXII which are prepared from the preferred starting compounds mentioned there are preferred.

Isocyanates of the formula XXXIII are known. Preferably, those mentioned in method 2a are used.

The diluents and catalysts used in process 2a ₃ are used.

In general, the compounds are presented XXXII in the diluent and at temperatures of 0 100 ⁰ C preferably 10 - 5 0 ⁰ C reacted with the isocyanates

The work-up is carried out in the usual way. Method 14

The reaction of the compounds of the formula XXXII with the acylating agents of the formula XXXV is optionally carried out in the presence of diluents and if appropriate in the presence of catalysts, if appropriate in the presence of acid acceptors.

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- 81 -

The course of the reaction may e.g. represented by the following formula scheme.

OH

C-CONH ₂ + CH ₃ COCl> A

N ^

CONHNH ₂ CONHNHCOCh ₃

Compounds of formula XXXII are new. They are prepared by the method described under 5. The compounds of the formula XXXII prepared from the preferred starting compounds mentioned there are preferred.

Compounds of formula XXXV are known. Prefers

29 compounds are used in which R is C. _, - alkylcarbonyl, optionally substituted phenylcarbonyl, C.-alkylsulfonyl, phenylsulfonyl.

In particular may be mentioned:

Benzoyl chloride, 3,4-dichlorobenzoyl chloride, 3-chlorobenzoyl bromide, acetyl chloride, acetic anhydride, propionyl chloride, methanesulfonyl chloride, benzoyl cyanide, tosyl chloride.

The diluents which may be used are those mentioned in method 2a.

Suitable acid acceptors are those mentioned in process 2a.

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The compounds of the formulas XXXII and XXXV are preferably reacted in the stoichiometric ratio (1: 1). A slight excess of one or the other component brings no significant advantages.

The acid acceptor is preferably used at least equimolar with respect to compound XXXV. It can also be used in excess as a diluent. Some acid acceptors, especially the tert. Amines such as triethylamine, pyridine, can be used in small quantities as catalysts and influence the reaction favorably.

The process is from 0 - 100 ⁰ C preferably 10 - 6O ⁰ C.

carried out.

The work-up is carried out in the usual way. Method 15

The reaction of the compounds of the formula XXXII with the carbonyl compounds of the formula XXXVII is optionally carried out in the presence of a diluent.

The course of the reaction may e.g. represented by the following formula scheme:

^0H -CCNH ₀ + O = C '

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For the compounds of formula XXXII the same applies in process 14.

The compounds of formula XXXVII are known.

Preference is given to using compounds of the formula

8 9

XXXVII in which R and R have the preferred meanings given above.

In detail may be mentioned:

Acetaldehyde, chloral, benzaldehyde, p-chlorobenzaldehyde, acetophenone, acetone, methyl ethyl ketone.

Suitable diluents are those mentioned in process 5.

The process is carried out at 2 0 - 12 0 ⁰ C preferably 5 0 - 10 0 ⁰ C performed.

The compounds of formula XXXII and XXXVII are used in approximately equimolar ratio. The carbonyl compounds of formula XXXVII can be used in excess and in part as diluents.

The workup is done in the usual way.

As catalysts, in addition to accelerating the reaction, acids such as p-toluenesulfonic acid, HCl, H-SO. or bases such as triethylamine, pyridine, NaOH.

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Method 16

The reaction of the compounds of the formula XXXIX with the compounds of the formulas XXXIII, XXXV, XXXVII is carried out as described for processes 13, 14 and 15.

The compounds of formula XXXIX are new. They are prepared as described in method 6.

Preference is given to using the compounds of the formula XXXIX which are prepared from the preferred starting compounds mentioned in Process 6.

The compounds XXXIX and XXXIII, XXXV ₇ XXXVII are each reacted in the stoichiometric ratio (1: 2). A slight excess of one or the other component brings no significant advantage.

Method 17

The reaction of the compounds of the formula XLI with trialkylsilyl compounds of the formula VIII is optionally carried out in the presence of diluents, if appropriate in the presence of catalysts.

The course of the reaction may e.g. represented by the following formula scheme:

0-B 'CV

(CH ₃ ) ₃ SiCN -> Cl-i \ / VC - CONHSi (CH ₃ J

CDNKSi (CH ₃ )

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The trialkylsilyl compounds are known. Preferred are those mentioned in Process 2b.

The compounds of the formula XLI are mentioned in process 2a "as starting materials of the formula II. Also preferred here are the preferred compounds of the formula II mentioned there. Further compounds of the formula XLI are those reaction products of the compounds of the formula II according to process 2 which contain at least one amide hydrogen.

Preference is given to those compounds of the formula XLI which result from the reaction of the preferred starting materials of process 2a.

Suitable diluents are those mentioned in process 2b. Optionally, it is also possible to work without a diluent.

The starting materials are at least equimolar, i. at least 1 equivalent of trialkylsilyl compound per amide to be silylated and optionally hydroxyl group used.

Preference is given to using an excess of the trialkylsilyl compound.

Suitable catalysts are the catalysts and / or acid acceptors mentioned in process 2b.

The work-up is carried out in the usual way.

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Method 18

The reaction of the compounds of the formula XXV and XLVI or XLVII is carried out in the presence of acids, if appropriate in the presence of diluents. The course of the reaction can be represented by the following reaction schemes:

0-Si (CH ₃ ) ₃ -

^X CN CONHC ₄ Hg-t

OSi (CH,), _rw OH

_b) λ / VC-CN + H ₂ C = C ^ ^J - ^ <^ - C ₄₉

^X CN CH ₃ CONHC ₄ H ₉ -t

The compounds of the formula XXV used are preferably those mentioned in process 10.

As alcohols of the formula XLVI are preferably called t-butanol, 2 ~ methyl-butanol-2.

Preferred olefins of the formula XLVII are isobutene, 2-methylpentene-1, 2,4,4-trimethylpentene-2, 2-methylbutene-2, 2-methylbutene-1.

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The reaction of the compounds of the general formula XXV with the tertiary alcohols of the general formula XLVI or the alkenes of the general formula XLVII takes place under the conditions of the so-called "Ritter reaction" or "Graf-Ritter reaction" (JACS 1Q, 4045 ( FIG. JACS Jl ' ⁴⁰⁴⁸ (1948); Methodicum Chimicum, Volume 6 (1974) It is surprising that the rather labile compounds of formula XXV are amenable to this reaction, since much more likely to be due to the acid treatment a cleavage of hydrogen cyanide.

The reaction may be carried out in the absence of a solvent, but is conveniently carried out in the presence of an organic solvent, in particular acids such as glacial acetic acid or optionally halogenated hydrocarbons such as dichloromethane may be used. Other useful solvents are ethers such as dibutyl ether, diisopropyl ether or anhydrides such as acetic anhydride.

The reaction temperature can be varied within wide limits. Preference is given to temperatures between -2 0 ° and + 5O ⁰ C in question.

Conveniently, the reactants are used in such amounts that come to one mole of the compounds of formula XXV excessively stoichiometric amounts of the alcohol or the alkene. For example, it is possible to use from 2 to 40 mol, preferably from 3 to 4 mol, of the alcohol or of the alkene per mole of the compound of the formula XXV.

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Also, the acid is suitably used in small excess amounts. For example, 2 to 20 moles, preferably 2.2 to 3 moles, of acid may be used per mole of the compound of formula XXV.

Sulfuric acid is preferably used as the acid, but other sulfonic acids such as benzenesulfonic acid may also be used.

After hydrolysis of the reaction mixture, the compounds of the formula XLV can be isolated in a manner known per se, for example by crystallization or extraction with subsequent crystallization or distillation.

Process variant b) (reaction with alkenes) may be preferred in some cases , for example when R represents a lower alkyl radical, as compared to variant a) (reaction with an alcohol).

Method 19

The reaction of the compounds of the formula XXII with alcohols or alkenes of the formulas XLVI and XLVII is carried out analogously to the conditions described in process 18.

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Method 21

The reaction of the compounds of the formula XLII with HCN, HCN-releasing compounds or trimethylsilyl cyanxd is optionally carried out in the presence of diluents, if appropriate in the presence of catalysts.

The course of the reaction may e.g. represented by the following formula scheme:

_Cl i ^ N (CH ₃ ) ₂ Clv CONH (CH ₃ ) ₂

^) C = O + HCN ~ -> C1- ^ ~ C

CN

(CH ₇ J ₇ SiCM-> \ J- CO-Si

CN

CH ₃ CON (CH ₃ J ₂

C-2

CH 1 -C-OH 2

^N CN

Cyanohydrins, for example acetone cyanohydrin or benzaldehyde cyanohydrin, are used as HCN-releasing substances.

The conversion of compounds of the formula XLII into compounds of the formula X proceeds according to the

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r- 90 -

known methods in the presence of small amounts of alkaline catalysts, such as sodium cyanide, potassium cyanide or tertiary amines such as triethylamine, and alkali and alkaline earth metal hydroxides and carbonates.

While the addition of molar amounts of HCN or trimethylsilyl cyanide is slightly exothermic already at room temperature and is complete after the addition of the reagents complete must be heated with the use of cyanohydrins some time to a complete. to achieve sales. It is also advisable to add more than 1 mol of cyanohydrin to 1 mol of <X / keto compound of the formula XLII. Preference is given to using 1.1-3, preferably 1.2-2, moles of cyanohydrin. The excess is distilled off again after the reaction has ended.

The reactions generally proceed without the presence of diluent, however, the use of solvents inert to the products and educts, e.g. Methanol, ethanol, isopropanol, toluene, chlorberizole, methylene chloride, carbon tetrachloride, acetonitrile, glutarodinitrile, dioxane and diethyl ether may be quite useful in some cases.

The reaction conditions for the reactions are very variable. Thus, e.g. HCN and trimethylsilyl cyanide are also used more than stoichiometrically, but a more than 10% molar excess no longer brings any advantages. Likewise, the reaction temperature is variable within wide limits, it can in the temperature

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be carried out at -5 0 to 300 ⁰ C, wherein at higher temperatures, either in the gas phase or in the liquid phase under pressure, the reactions are carried out. But even here there is no significant advantage over the preferred experimental parameters described first.

Method 23

The method is described in an older not yet belonging to the prior art application of the applicant (German Application P 31 40 275.5).

The process for the preparation of the compounds of the formula XVII can be carried out by the following methods of Pinner (A. Pinner, the imido ethers and their derivatives, Berlin 18 82).

In this case, the nitrile group-containing compound is generally reacted either with hydrochloric acid or with sulfuric acid in alcoholic solution and water.

In the following both methods are described by way of example, but without limiting the generality of the method.

Saponification with sulfuric acid:

For every 1 mole of the compound of the formula XXV, 100-1000 g concentrated sulfuric acid, 2-25 moles

2 kohols the formula R OH and 1 mole of water used.

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A greater deviation from the stoichiometry in the dosage of the amount of water leads to yield losses. A possible water content of the starting materials {alcohol and sulfuric acid) can be taken into account in the amount of water to be added. The batch solution is performed at temperatures of 0 - 15O ⁰ C, preferably 20 - 100 ^0C, particularly preferably 60 - 9O ⁰ C, stirred for 1-20 h. Optionally, it is possible to work under elevated pressure. The mixture is then stirred into ice-water and extracted cold with a customary organic solvent such as methylene chloride, toluene, ethyl acetate and the product optionally purified by distillation.

However, the method variant in which alcohol, acid and water are initially introduced and then the compounds of the formula XXV are added is particularly preferred.

The following is an example of the reaction procedure for the inverse Pinner esterification with hydrochloric acid are described:

The absolute alcohol is in 2 - 20 times the molar excess - based on the compound of formula XXV - presented and saturated at -10 to +10 ⁰ C with HCl gas. In this case, at least 2 moles of HCl must be absorbed for 1 mole of the compound of formula XXV. At -2 0 to + 1O ⁰ C, preferably at -1O ⁰ C, the reaction component of the formula XXV is added dropwise and then about 1 hour at max. 3O ⁰ C stirred before with the stoichiometric

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Amount of water based on CN groups used, optionally diluted in the alcohol, is added.

Excessive excess or deficiency in the amount of water leads to yield losses.

After stirring for about 1 hour at 0 - 5 0 ⁰ C, is worked up in the usual way.

Distillation of the compounds of the formula XVII should be dispensed with if their boiling points significantly exceed 160 ^° C. under distillation conditions.

Method 25

The hydroxy-malonated diamides of the formula XLIV are the subject of a not yet belonging to the prior art application of the applicant. They are obtained for example by saponification of Trimethylsilyloxymaionsäuredinitrilen with inorganic acids such as sulfuric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid and boric acid, preferably sulfuric acid and hydrochloric acid, at temperatures between -15 ⁰ C and 100 ⁰ C, preferably between 0 ⁰ C and 80 ⁰ C, optionally using water as

Diluent (German Application No. P 31 40 275.5).

The Trimethylsilyloxymalonsäurenitrile to be used as precursors for the preparation of the novel compounds of formula XXV are known. (Chem. Ber. 106 , (1973), Tetrahedron Letters 17, 1449-1450 (1973) or

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can be easily prepared according to the methods given there.

As examples of the starting materials of the formula (II) may be mentioned:

Phenylhydroxy-malonic acid diamide, 2-, 3-, 4-chlorophenylhydroxy-malonic acid diamide, 2,3-dichlorophenyl-hydroxymalonic acid diamide, 3,4-dichlorophenyl-hydroxy-malonic acid diamide, 3,5-dichlorophenyl-hydroxy-malonic acid diamide, 2,4- Dichloro-phenyl-hydroxy-malonic acid diamide, 2,5-dichlorophenyl-hydroxy-malonic acid diamide, 2,6-dichlorophenyl-hydroxy-malonic acid diamide, 2-, 3-, 4-nitrophenylhydroxy-malonic acid diamide, 2-chloromethylphenyl-hydroxymalonic acid diaxide, 2, 3, 4-Trifluoromethylphenyl-hydroxymalonic acid diamide, 2-, 3-, 4-methoxyphenyl-hydroxy-malonic acid diamide, 2,6-dimethoxyphenyl-hydroxy-malonic acid diamide, 2-, 3-, 4-tolyl-hydroxy-malonic acid diamide, 2-, 3 , 4-trifluoromethoxyphenyl-hydroxy-malonic acid diamide, 2-, 3- and 4-fluorophenyl-hydroxymalonic acid diamide.

The active compounds are suitable for good plant tolerance and favorable toxicity to warm-blooded animals for controlling animal pests, in particular insects, arachnids, which occur in agriculture, in forests, in the protection of stored products and material, and in the hygiene sector. They are effective against normally sensitive and resistant species as well as against all or individual stages of development. The above mentioned pests include:

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From the order of isopods e.g. Oniscus asellus, Armadillidium vulgaris, Porcellio scab.er.

From the order of diplopoda e.g. Blaniulus guttulatus.

From the order of Chilopoda e.g. Geophilus carpopha-5. gus, Scutigera spec.

From the order of Symphyla e.g. Scutigerella immaculata.

From the order of Thysanura e.g. Lepisma saccharina.

From the order of Collembola e.g. Onychiurus armatus. From the order of Orthoptera e.g. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus diff erentialis ,, Schistocerca gregaria

 From the order of the Dermaptera e.g. Forficula auricularia.

From the order of Isoptera e.g. Reticulitermes spp ..

From the order of the Anoplura e.g. Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.

From the order of Mallophaga e.g. Trichodectes spp., Damalinea spp.

From the order of Thysanoptera e.g. Herculothrips femoralis, Thrips tabaci.

From the order of Heteroptera, e.g. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of Horaoptera e.g. Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii,

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Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp.

From the order of Lepidoptera e.g. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp. Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp. , Chilo spp., Pyrausta nubilalis, Ephestia kuehniel-Ia, Galleria mellonella ,. Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

From the order of Coleoptera e.g. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonia.

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nomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assirailis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides,

Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphiraallon solstitialis, Costelytra zealandica

 From the order of Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Ve spa spp.

From the order of Diptera e.g. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp.,

Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis Capitata, Dacus oleae, Tipula paludosa.

From the order of siphonaptera e.g. Xenopsylla cheopis, Ceratophyllus spp.

From the order of the arachnids, e.g. Scorpio maurus, Latrodectus mactans

 From the order of Acarina e.g. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyornma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp , Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus

spp ..

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The active compounds can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, active substance-impregnated natural and synthetic substances, microencapsulations in polymeric substances and in seed coating compositions, furthermore in formulations with Fuel packs, such as smoke cartridges, cans, spirals, etc., as well as ULV ₄ -KaIt- and warm mist formulations.

These formulations are prepared in a known manner, e.g. by mixing the active compounds with extenders, that is to say liquid solvents, liquefied gases under pressure and / or solid carriers, if appropriate using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-forming agents. In the case of using water as an extender, e.g. also organic solvents can be used as auxiliary solvents. 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, e.g. 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; with liquefied gaseous diluents or carriers, such liquids are

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means which are gaseous at normal temperature and under normal pressure, e.g. Aerosol propellants, such as halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; as solid carriers there are suitable: e.g. 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:

e.g. crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite and synthetic granules of inorganic and organic flours and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; suitable emulsifiers and / or foam formers are: e.g. nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. Alkylarylpolyglycol esters, alkylsulfonates, alkylsulfates, arylsulfonates and protein hydrolysates; suitable dispersants are: e.g. Lignin-sulphite liquors and methylcellulose.

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

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes.

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Substances and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

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

The active compounds according to the invention can be present in their commercially available formulations as well as in the formulations prepared from these formulations in admixture with other active ingredients, such as insecticides, attractants , sterilants, acaricides, nematicides, fungicides, growth-regulating substances or herbicides. The insecticides include, for example, phosphoric esters, carbamates, carboxylic esters, chlorinated hydrocarbons, phenylureas, substances produced by microorganisms, among others

The active compounds according to the invention can furthermore be present in their commercial formulations and in the formulations prepared from these formulations in admixture with synergists. Synergists are compounds which increase the effect of the active ingredients without the added synergist itself having to be active.

The active substance content of the application forms prepared from the commercial formulations can be varied within wide ranges. The drug concentration

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The application forms may be from 0.0000001 to 95% by weight of active ingredient, preferably between 0.00 01 and 1% by weight.

The application is done in a custom forms adapted to the application.

When used against hygiene and storage pests, the active ingredients are characterized by an excellent residual effect on wood and clay and by a good alkali stability on limed substrates.

The active compounds according to the invention are also suitable for controlling ecto- and endoparasites, preferably of ectoparasitizing insects in the field of animal husbandry and animal breeding.

The application of the active compounds according to the invention is done here in a known manner, such as by oral application, by dermal application in the form of, for example, diving (dipping), spraying (spraying), pouring (pur-on and spot-on) and powdering.

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Preparation Examples

Example 1 Method 2a

30 g (0.114 mol) of 3,4-dichloro-phenyl-hydroxy-malonic acid diamide are initially charged in 60 ml of dimethyl sulfoxide. Then 6.38 g (0.144 mol) of potassium hydroxide in 150 ml of water, then 16.1 g (0.114 mol) of methyl iodide are added dropwise. The reaction is exothermic: The temperature rises to about 50 ⁰ C. It is allowed to cool and stirred for 16 hours at 20 ⁰ C after. The precipitated solid is filtered off with suction and washed with water and then with petroleum ether.

After recrystallization from Essigester 14.1 g (44.3% of theory) is obtained 2- (3 _y 4-dichlorophenyl) -2-methoxy-malonamide a melting point of 211 to

Example 2 Method 2a

Cl-AO) -C-CONH

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2 6.3 g of 3,4-Dichlorphenylhydroxyrnalonsäurediaraid was dissolved in 50 ml of pyridine and treated at below 3O ⁰ C with 17.1 g of o-chlorobenzoyl chloride. After one hour, the mixture was stirred into cold HCl, the precipitate taken up in ethyl acetate, extracted by shaking and worked up. There remained 26.5 g of crude product, which was recrystallized from 400 ml of ethanol. There were 13 g of pure 3,4-dichlorophenyl- (2-chlorobenzoyloxy) -malonsäurediamid, mp. 220 ⁰ C obtained.

Example 2a

Analogously to the above procedure, 3,4-dichlorophenyl- (3,4-dichlorobenzoyloxy) -malonic acid diamide of mp 237 ^° C. (decomposition) was obtained.

Example 3 Method 2a_

CHOK-CONH ₂

13.1 g of 3,4-Dichlorphenylhydroxymalonsäurediamid- were heated in 200 ml of benzoyl chloride at 110 ⁰ C for 9 hours. It was then cooled to 5 ⁰ C, - filtered off with suction, the precipitate washed with toluene and then recrystallized from 550 ml of isopropanol. There were 10 g of 3, ^ - Dichlorphenylbenzoyloxymalonsäurediamid isolated: mp 225 ⁰ C with decomposition.

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Example 4

Method 2a,

10

Cl- (O) -C-CONH ₂ CONH ₂

131 g of 3,4-Dichlorphenylhydroxymalonsäurediamid, 85 0 ml of tetrahydrofuran and 750 ml of acetyl chloride were heated for 4 hours at reflux. After cooling, the precipitate was filtered off with suction and washed with i-propanol. There were 115 g of 3,4-Dichlorphenylacetoxymalonsäurediamid com mp. = 206 ⁰ C obtained.

Example 5

Method 2a,

0-SO ₂ -NH-CH-

CONH-

15

2 6.3 g of 3,4-dichlorophenylhydroxymalonic acid diamide were dissolved in 70 ml of pyridine and admixed at room temperature with 18 g of methylsulfamoyl chloride.

After 3 hours, it was stirred into cold HCl, extracted with ethyl acetate and the organic phase was worked up. There were 17 g of 3,4-dichlorophenylmethylsulfamoyloxymalonsäurediamid of mp. = 124 ⁰ C isolated.

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Example 6 Method 2a_

0-C-Wd (Q)

-0-COOCH ₃ COOCH ₃

22.4 g Phenylhydroxymalonsäuredimethylester were dissolved in 100 ml of ethyl acetate, with 11.9 g of phenyl isocyanate and. 2 drops of dibutyltin dilaurate heated for 3 hours at reflux. After cooling, the product was filtered off with suction and the residue was recrystallized from toluene. There remain 11 g of phenyl (phenylaminocarbonyloxy) -malonate; Mp 17O ⁰ C (with strong decomposition).

Example 7 Method 2a

CONH-

26.3 g of 3,4-Dichlorphenylhydroxymalonsäurediamid were dissolved in 350 ml of ethyl acetate at 65 ⁰ C and slowly treated with a solution of 19.7 g of p-toluenesulfonyl isocyanate. After 1 h at 7O ⁰ C content η had been, was cooled and filtered with suction. 14 g of 3,4-dichlorophenyl-p-toluenesulfonylaminocarbonyloxy-malonic acid diamide (mp 178 ° C., decomposition) were obtained. From the mother louse was further isolate product.

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Example 8

OC-NH -C-CONH ₂ CONH ₂

Cl

Method 2a.

8.2 g of Phenylhydroxymalonsäurediamid was added in 3 0 ml of ethyl acetate with 0.5 g of zinc octoate and 4.45 g of 3-chlorophenyl isocyanate and kept at 5O ⁰ C for 30 min. After cooling, the mixture was filtered off with suction and recrystallized from acetone. There remain 5.6 g of phenyl (3-chlorophenylaminocarbonyloxy) -malonsäurediamid, mp. 196-198 ° C obtained.

According to the above instructions, the following isocyanate reaction products were obtained:

0-C-NH-CH ₃

Mp: 199 ^° C. acetonitrile

O) OC-NH-C-fo), UCONH ₂ > ^

Cl

189-191 ° C

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O 'O

0-C-NH-CO-CH ₂ -CH (CH ₂ ) ₃ CH ₃ ¹ CONH ₂ '^ CONH ₂ ° ^2Ε =

ίο

: ι

C ₂ H ₅

Mp. =

Cl

o-c-Zh-nh)

I ^ CONH2 ^ - ^y

he

Cl

- 185 ° C

Mp = 197-99 ° C (n-butanol)

_0-C-NHCH3, LCONH ₂

^N CONH 2

OCF ₃

• mp = 191 - 192 ° C

0-C-NH-CH ₃ 'CONH ₂

VZONH 2

CF

Mp = 176 - i77 ° C

0-CNH-C ₄ H ₉ 'CONH ₂ V ^N CONH 2

Cl

Mp = 189-191 ⁰ C

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! I

CONH;

Cl

Cl

Cl

- 108 mp = 193-194 ° C

0-C-NHCH ₃

C-CONH ₂

. CONH ₂ mp = "205 ⁰ C (decomposition:

0-C-NHCH ₃ I CONH ₂

NO ₂

Cl mp = 200 ^° C (decomposition)

19a)

Cl

OC-NH- <5) ~C1 -C-CONH ₂ Fp.

COOCH ₃

Cl

-CONHCO-

Cl

Q V-C-CONH. CONH-

= 205 - 208 ⁰ C

Cl mp = 199 ° C

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Example 2 0 Process 3

OH CL - ^) - CCOOCH ₃

Cl CONH ₂

in 400 g of sulfuric acid (96%) was at max. 40 ⁰ C added dropwise 210 g of 3,4-dichlorophenyl-trimethylsilyloxy malonic acid ethyl ester nitrile. The mixture was stirred for 1 hour at room temperature and then stirred into ice water.

The first greasy, then crystallizing precipitate was taken up in ethyl acetate, washed ge-O, dried and concentrated.

By recrystallization from isopropanol was 3,4-dichlorophenyl-hydroxy-malonic acid methyl ester amide melting point 132 - 133 ⁰ C obtained.

Example 21 Method 3

OH

CONH

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Analogously to the above example, from 187 g of tert-butyltrimethylsilyloxy-malonic acid methyl ester nitrile by saponification in 500 g of H-SO. 55 g tert-Butylhydroxymalonsäuremethylesteramid hergestel1t. Melting point 102-103 ⁰ C (from benzine).

Example 22 Method 3

95 g of phenyl-hydroxy-malonsäuremethylesternitril be at 3O ⁰ C to 500 g of H ₃ SO ₄ dropwise.

After stirring for 30 minutes at room temperature, was stirred into ice water, taken up with methylene chloride, washed and concentrated. The residue was recrystallized from toluene. There were obtained 72 g of phenyl-hydroxy-malonic acid methyl ester amide melting point 123 - 4 ⁰ C.

Example 23 Method 3

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- Ill -

To 250 ml H ₃ SO ₄ conc. were added dropwise at 40 ⁰ C 63 g Phenyltrimethylsilyloxymalonsäuredimethylamidnitril. After stirring, the temperature for 9 h was maintained at 4O ⁰ C, was poured onto ice, extracted with CH_C1 "and worked up the organic phase. There remained 31 g residue, which was recrystallized from i-propanol. There remain 2 6.2 g Phenylhydroxymalonsäureamiddimethylamid; M.p. 13 7 -8 ⁰ C.

Example 24 Method 3

In 3 00 ml H ₃ SO ₄ conc. was at max. 40 ⁰ C 90 g Phenyltrimethylsilyloxymalonsäuremorpholidnitril, After 2.5 hours at 4O ⁰ C was stirred into ice water and extracted 3x with methylene chloride. The organic phases were combined, washed with a little water and the solvent was distilled off, with high vacuum being applied towards the end. There remain 57 g glassy product, which was identified spectroscopically as Phenylhydroxymalonsäuremorpholidamid.

Example 25 Method 3

CONH:

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10 g Phenyltrimethylsilyloxymalonsäureanilidnitril were added at 3O ⁰ C in 100 ml of concentrated hydrochloric acid. The suspension was then heated for 2 hours to 5 0 ⁰ C, the residue taken up in methylene chloride, washed and worked up. There remained 5 g of glassy crude product, which was recrystallized from toluene. It was possible to isolate 4 g of phenylhydroxymalonic acid anilidamide. Mp from HO ⁰ C with decomposition.

Example 26 Method 4

CONHCOCH ₃

: Ovc:

^ COOCH ₃

To a solution of 88.6 g of glacial acetic acid and 74 ml H_SO. conc. was added dropwise at 40 - 5O ⁰ C 94 g Phenylhydroxymalonsäuremethylesternitril. After 1 hour, the reaction solution was added to ice-water and extracted with methylene chloride. After working up the organic phase, the residue was recrystallized from i-propanol. There remained 50 g of a mixture of Phenylhydroxymalonsäuremethylesteramid and Phenylhydroxymalonsäuremethylesteracetylamid in the approximate ratio 1: 1, as was apparent from the spectroscopic data.

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By treating the substance mixture with NH 2 in methanolic shear solution at 30 - 5O ⁰ C for 2 hours Phenylhydroxymalonsäurediamxd of mp. 15 9 ⁰ C was obtained.

Example 2? Method 5

⁰ ^ CONH ₂ "CONHCH ₃

In a solution of 42 g Phenylhydroxymalonsäuremethylesteramid in 400 ml of methanol was introduced 4 hours at reflux temperature methylamine. After being concentrated, by recrystallization from ethanol, 30 g of phenylhydroxymalonic acid amide methylamide (mp = 128 ° C.) was obtained.

Example 2 8 'Method 5

C.

-C-NH-CH ₂ -CH ₂ -OHO OCH _n

20.9 g of phenylhydroxymalonic acid methyl ester amide 6.1 g of ethanolamine and 60 ml of methanol were refluxed for 3 hours. After concentration (towards the end in a high vacuum) 2 4 g of highly viscous residue remained, which was identified spectroscopically as the desired Phenylhydroxymalonsäureamid-ß-hydroxyethylamide.

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Example 29 Method 5

OH 0 Q VCC-NH-NH C * ⁰

62.7 g of phenylhydroxymalonic acid methylesteramide, 15 g of hydrazine hydrate and 200 ml of methanol were heated at reflux for 4 hours. It was concentrated to 6O ⁰ C bath temperature in a water-jet vacuum, mixed with toluene and concentrated again, towards the end in a high vacuum. There remained 65 g of glassy residue, which proved to be spectroscopically Phenylhydroxymalonsäureamidhydrazid.

10. Example 30 Procedure 6

O.

OH "

"C-NH-NH ₂

^ C-NH-NH,

Il

22.4 g of phenylhydroxymalonic acid dimethyl ester and 10 g of hydrazine hydrate were refluxed in 100 ml of methanol for 5 hours. The mixture was then concentrated at 5 0 ⁰ C, towards the end under high vacuum. There remained 2 4 g of a glassy residue, which was recrystallized from water. There were obtained 14 g phenylhydroxymalonic acid bis-hydrazide mp 159 ° C (decomposition).

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Example 31 Method 6

OH '--CONH-NH ₂

20.9 g Phenylhydroxymalonsäuremethylesteramid and 25 g of hydrazine hydrate were heated in 150 ml of ethanol for 12 hours at reflux. It was then concentrated and recrystallized from 75 ml of water. There remained 13 g phenylhydroxymalonic acid bishydrazide, mp. 159 ° C (decomposition.

Example 32 Method 6

14.7 g of 3,4-Dichlorphenylhydroxymalonsäuredimethylester were dissolved in 100 ml of methanol and introduced at 6O ⁰ C for 1 hour methylamine. It was completely concentrated and the crystalline residue was recrystallized from 100 ml of ethanol. 12 g of 3,4-dichlorophenylhydroxymalonic acid dimethylamide (mp = 158-6O ⁰ C) were obtained.

Example 32a

Analogously to the above procedure 3,4-Dichlorphenylhydroxymalonsäuredineopentylamid (mp = 94 - 95 ⁰ C) was obtained.

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Example 33 Method 7

COONa '

5.41 g Phenylhydroxymalonsäuremethylesteramid were stirred with 25.9 ml of aqueous In NaOH solution for 2.5 hours at room temperature. The reaction solution became almost homogeneous, the pH dropped to 6. After filtration, the mixture was concentrated, towards the end in a high vacuum. IR, NMR and MS (FAB) confirmed the presence of the monosodium salt of the phenylhydroxymalonic acid monoamide.

Example 33a

The free acid of the compound of Example 32 was obtained by suspending the salt of Ex. 33 in methylene chloride and treating with HCl gas.

Example 34 Method 8

COONa

11.2 g of 3,4-Dichlorphenylhydroxymalonsäuredimethylester were stirred with 76.6 ml of aqueous In NaOH solution at room temperature until the solution had a pH of 6. It was then filtered off and concentrated.

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IR, NRM and MS (FAB) confirmed the presence of the disodium salt of 3,4-dichlorophenyl hydroxymalonic acid.

Example 35 Method 9

2 6.5 g of dimeric benzoyl cyanide were at 75 - 8O ⁰ C to a solution of 12 g of glacial acetic acid and 1.5 ml of H-SO ₄ conc. dripped. After half an hour, it was poured onto ice, shaken out with methylene chloride, and the organic phase was washed and worked up. The residue was recrystallized first from isopropanol, then from ethanol. There remained 10 g of benzoyl-benzoyloxymalonsäurebisacetylamid, mp. 186 - 87 ⁰ C.

Example 36 Method 2a

CI _n OSCECl ₂

C-CONH ₂ CONH ₂

13 g of 3,4-dichlorophenylhydroxymalonic acid diamide and 8.5 g of dichlorofluoromethylsulfonyl chloride were refluxed in 100 ml of dioxane for 10 hours. After concentration, 20 g of 3,4-dichlorophenyl-dichlorofluoromethylsulfenyloxy-malonsäurediamid of mp. 12O ⁰ C decomposition).

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Example 37 Method 10

Cl OH O '

In 67 g of formic acid and 16.8 ml I ^ SO ^ concentrated, 77.3 g of 3,4-Dichlorphenyltrimethylsilyloxymalonsäuredinitril were added dropwise at 25 ⁰ C and held for 28 hours at this temperature, with occasional stirring. The mixture was then stirred into ice-water, taken up with ethyl acetate and the organic phase was washed until neutral. After working up, 48 g of crude product remained, which was recrystallized from isopropanol. According to spectroscopic investigations (IR, H and C ¹ -NMR, MS (DCI), 3,4-dichlorophenylhydroxymalonic acid amide formylamide was present in addition to 3,4-dichlorophenylhydroxymalonic acid diamide in an approximate ratio of 1: 1.

Example 38 Method 10

To a solution of 72 g of glacial acetic acid and 60 ml of H-SO. conc. were added dropwise at 40 - 5O ⁰ C 92 g phenyltrimethylsilyloxymalonsäuredinitril. After 2 hours,

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DE poured the viscous solution on ice, stirred well and filtered with suction. There remained 53 g of crude product, which was recrystallized from water. Ss remained 40 g phenylhydroxymalonic acid amide acetylamide; M.p. 21O ⁰ C (decomposition).

Example 38a

3,4-Dichlorphenylhydroxymalonsäureamidacetylamid - mp. 2 02 ⁰ C (decomposition) - synthesized analogously to the above method.

Example 39 Procedure 11

11

CI _n 0-C-CH ₃ 0 Cl- (O) -C-C-NH-C-CBL

13.2 g 3,. 4-Dichlorphenylhydroxymalonsäuradiamid were heated in 60 ml of acetic anhydride to 8O ⁰ C and at this temperature 6 ml of a solution of 0.3.g H "SO, conc. in 100 ml of acetic anhydride. It was 10 min. further stirred at 8O ⁰ C, then cooled to 20 ⁰ C, poured onto ice and the crude product was filtered off with suction. After drying, trituration in methylene chloride and suction filtered. There remained 8 g of 3,4-dichlorophenylacetoxy-malonsäureamidacetylamid, mp. 202 ⁰ C (decomposition).

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Example 40 Procedure

Cl 0-C-CH ₃ O > ^ \ i "Cl- \ O / -C-C-NH-C-CH ₃

Lo ^ o

^ NH-C-CH ₃

Il

52.6 g of 3,4-dichlorophenylhydroxymalonic acid diamide were suspended in 130 ml of acetic anhydride and treated with 0.3 ml of H 2 SO 4. conc. added. It was heated to 80 ° C for 45 min, resulting in a clear solution. The precipitated after cooling crystals were filtered off with suction, triturated with water and a little i-propanol. There remained 55 g of 3,4-dichlorophenyl-acetoxy-malonic acid bisacetylamide, mp. 170 ⁰ C.

Example 40a

Analogously to the above example, 12 g of 4-chloro-3-methylphenylhydroxymalonic acid diamide were reacted. There were obtained 14.3 g of 4-chloro-3-methylphenyl-acetoxymalonsäurebisacetylamid, mp. 169-171 ° C.

Example 41 Procedure

Cl-ZO) -C-CONH-C-CH- ^ NH-C-

11

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- 121 -

7.7 g of 3,4-dichlorophenylbenzoyloxymalonic acid diamide were dissolved in 60 ml of acetic anhydride with 3 drops of H 2 SO 4. conc. and heated to 75 ⁰ C for 7 hours. It was then poured into ice-water, filtered off and recrystallized from i-propanol. 4 g of 3,4-dichlorophenylbenzoyloxymalonic acid bisacetylamide were obtained, mp 198 ^° C. (decomposition).

Example 42 Procedure 12

0-C-CH ₃ C-NH-C

CQOCH,

2 0.9 g Phenylhydroxymalonsäuremethylesteramid were dissolved in 150 ml of acetic anhydride at 60 ⁰ C and with 3 drops of H ₂ SO, conc. added. The temperature rose to 75 ⁰ C on. It was heated for a further 2 hours to 8O ⁰ C, then concentrated, taken up with toluene and washed neutral with water and NaHCO, solution. After working up, 25 g of oil remained, which, according to spectroscopic data, consisted of phenylacetoxymalonic acid methyl ester acetylamide.

Example 43 Method 13

OH 0 0

- C-NH-NH-C-NH- (O /

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'' Λ T rt

ο? r · 'τ.,' f>

- 122 -

26.4 g of phenylhydroxymalonic acid amide hydrazide were dissolved in 50 ml of abs. Dissolved dioxane and with a solution of 15 g of phenyl isocyanate in 15 ml of abs. Dioxane added. The temperature rose to 40 ⁰ C and it precipitated out. It was filtered off with suction and the residue was boiled with 500 ml of water. There remained 27 g of not completely clean Phenylhydroxymalonsäureamid- (phenylaminocarbonyl) hydrazide (mp 199 ⁰ C).

Example 44 Method 14

1Π OFT "

, CONH-NH-C-CH ₃

CONH ₂

21.2 g Phenylhydroxymalonsäureamidhydrazid was dissolved in 100 ml of dioxane, added 10.3 g of triethylamine and 8 g of acetyl chloride was added dropwise. The mixture was stirred for 1 hour at room temperature, the precipitate was filtered off with suction and the mother liquor was concentrated. Thereafter, 28 g of unclean crude product, which was taken up in ethyl acetate and washed with a little water remained. After removal of the solvent in a high vacuum at 60 ⁰ C bath temperature Phenylhydroxymalonsäureamidacetylhydrazid remained as a glassy residue.

Example 45 Procedure 15

OH O -C - C-NH-N = C

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20 g of phenylhydroxymalonic acid amide hydrazide were refluxed in 100 ml of acetone for 3 hours. The . Crystals were filtered off and recrystallized from ethanol. There were 15 g Phenylhydroxymalonsäureamid- (2-propylidene) hydrazide (mp. 139 - 201 ⁰ C).

Example 4 6 Method 16

11.2 g Phenylhydroxymalonsäurebishydrazid was heated in 100 ml of acetone for 4 hours at reflux. It was then concentrated, towards the end in a high vacuum. There remained 13.8 g of crude phenylhydroxymalonic acid bis (2-propylidene hydrazide) as a highly viscous residue.

Example 47 Procedure 17

0SKCH ₃ ) ₃ ^C S)

CL CO-NH-

3 g (0.0114 mol) of 3,4-dichloro-phenyl-hydroxy-malonamide, 1.12 g (0.114 mol) of trimethylsilyl cyanide and 0.9 g (0.0114 mol) of pyridine are heated to 10 ⁰ C for 6 hours ( Bath temperature). After removal of the pyridine in a water-jet vacuum, the residue is recrystallized from petroleum ether.

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This gives 3.45 g (90.3 g of theory) of 2- (3,4-dichlorophenyl) -2-trimethylsilyloxy-malonamide of melting point 156 ^° C.

Example 48 Procedure 17

0Si <CH ₃ ) ₃ --CO-NH-Si (CH ₃ ) 3

CL CO-NH-SiCCH ₃ ) 3

30 g (0.114 mol) of 3,4-dichloro-phenyl-hydroxy-malonamide, 46 g (0.464 mol) of trimethylsilyl cyanide 'and a few drops of pyridine are mixed and heated for 12 hours to the boiling point. After cooling, filtered off with suction and washed with a little cold petroleum ether.

4 8.6 g (89% of theory) of 2- (3,4-dichlorophenyl) -2-trimethylsilyl-l, 3-bis-trimethylsilylmalonic acid of melting point 107 to 109 ^° C. are obtained.

The procedure was as in the above example, but without pyridine as a catalyst, but in 130 ml of dioxane as a solvent. After concentration and Ümkristallisatxon from benzene, the desired end product was obtained here.

Analogously to Example 4 8, the following compounds of the formula (I) can be prepared:

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CI)

Example RRR R ' R Melt no. Point

⁰ C

49 4-Cl HH-Si (CH ₃ ) ₃ -Si (CH ₃ J ₃

50 3-Cl 5-Cl H -Si (CH ₃ ) ₃ -Si (CH ₃ J ₃ 112-113 50a 3-Cl 3-Cl 5-Cl -Si (CH ₃ J ₃ -Si (CH ₃ 9 ₃

Example 51 Procedure 17

0-Si (CH ₃ ) 3. C-CONHSi (CH ₃ ) 3 COOCH ₃

4.2 g of Phenylhydroxymalonsäuremethylesteramid were heated with 8 g of trimethylsilyl cyanide and 1 drop of pyridine for 8 hours at reflux, the condenser was preheated to 4O ⁰ C to separate the resulting hydrocyanic acid. Subsequently, at 4O ⁰ C bath temperature. narrowed, towards the end in Hcchvakuu. It remained ^; a viscous oil, which according to spectroscopic studies of phenyltrimethylsilyloxymalonsäuremethylestertrimethylsilylamid existed.

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Example 52 Procedure 18

O C-NH-C (CH ₃ ) ₃

QVC

"" ** C-NH-C (CH ₃ ) ₃

To a solution of 69 g Phenyltrimethylsilyloxyrnalonsäuredinitril and 89 g tert. Butanol in 150 ml of methylene chloride was at 0 - 5 ⁰ C 100 g of sulfuric acid conc. dropwise. Subsequently, the exothermic reaction at 4O ⁰ C and was kept for another 30 min. stirred at 3O ⁰ C stirred. The reaction mixture was added to ice and shaken out with more methylene chloride. After working up the crude product (98 g) was distilled. It was possible to obtain 8 9 g of phenylhydroxymalonic acid bis-tert-butylamide. Kp _Q _ = 116-118 ⁰ C, mp. 99 - 100 ⁰ C.

Example 53 Method 19

O CNHC (CH ₃ ) ₃

(CH ₃ ) 3C-CO-CO-C (CH ₃ ) ₃ CNHC (CH ₃ )

Il ³

90 g of dimeric pivaloyl cyanide, 120 g of tert. Butanol 150 ml of methylene chloride and 122 g of sulfuric acid were reacted as in Example 52.

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13.6 g of tert-butyl O-tert-butylcarbonyloxymalonic acid bis-tert-butylamide were isolated.

Kp = 105-106 ⁰ C; Mp 63-64 ⁰ C

 υ, ζ

Example 54 Method 21

To 82 g Phenylglyoxylsäuremethylester and 1 ml of triethylamine were added dropwise 13.5 g of hydrogen cyanide at 25 - 30 ⁰ C. Based on the spectroscopic data, phenyl-hydroxy-malonic acid methylesteritrile had formed.

Example 55 Method 21

OSi (CH ₃ ) ₃

To 8 8.5 g Phenylglyoxylsäuredimethylamid and 1 ml of triethylamine 50 g 15-Trimethylsilylcyartid was added dropwise at 30 ⁰ C under ice cooling. After 45 min. was degassed in a water jet vacuum. IR, NMR, MW, GC confirmed the structure of phenyl trimethylsily.loxymalonic acid dimethylamidonitrile.

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Example 56

Analogously to Example 55 phenylglyoxylic acid morpholide was reacted to Phenyltrimethylsilyloxymalonsäuremorpholidnitril.

Example 57 Method 21

9Si (CH ₃ J ₃ , 0

52.3 g Phenylglyoxylsäureanilid were in 100 ml of abs. Methylene chloride dissolved, mixed with 3 ml of triethylamine and at max. 3O ⁰ C 23 g trimethylsilyl cyanide was added dropwise. Stirring was continued for 3 hours at room temperature and then the solvent was distilled off. De: residue was recrystallized from benzine; There were obtained 70 g Phenyltrimethylsilyloxymalonsäureanilidnitril, mp 106-107 ⁰ C.

Example 5 8 Method 21

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To 147.8 g of 3,4-dichlorophenylglyoxylsäuremethyiester and 0.5 ml of triethylamine were under ice cooling at max. 55 ^° C. 62.8 g of trimethylsilyl chloride were added dropwise. 210 g of 3,4-dichlorophenyl-trimethylsilyloxymalonic acid methyl ester nitrile were obtained. IR, NMR and MS confirm the presence of the substance.

Example 5 9 Method 21

OSi (CH ₃ J ₃

(CH 1 KC-C-C CN

Analogously to the above example, 197.8 g of tert-butyltrimethylsilyloxy-malonic acid methyl ester nitrile were prepared from 116.8 g of tf-keto-3,3-dimethylbutyric acid methyl ester, 0.5 ml of triethylamine and 81 g of trimethylsilyl cyanide.

Example 60 Method 23

COOCH

100 ml abs. Methanol were saturated at 1O ⁰ C with about 80 g of hydrochloric acid. Was then added dropwise from -10 to -5 ⁰ C, 131.5 g of phenyl-trimethylsilyloxy-rnalonsäuremethylesternitril. The homogeneous solution was stirred for 1 hour at 10 - 15 ⁰ C, where they

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became two-phase. Subsequently, 9 g of water, diluted with 50 ml of methanol, added dropwise and stirred at 20 ° C for 2 hours.

It was concentrated, taken up with methylene chloride, washed with water, dried, concentrated by evaporation and distilled.

It was 84 g phenyl-hydroxy-malonsäurebismethylester Kp _n _ = 126-28 ⁰ C obtained.

Example 61 Procedure 2 3

/ ~ Λ? ^Η

Cl- <Ο / -C-COOCH- *

\ ^ ^ ^ / Ι J

/ ~ ^ COOCH,

³

320 ml abs. Methanol was saturated at 10 ⁰ C with about 210 g of hydrochloric acid. At -10 ⁰ C, 300 g of 3,4-dichlorophenyl-trimethylsilyloxy-malononitrile were added dropwise, stirred at 10 - 15 ⁰ C for 1 hour and at 15 ⁰ C. with 36 g of water, diluted with 50 ml of methanol. Then 1 hour at max. 3O ⁰ C stirred, filtered with suction from the precipitated crystals and concentrated the filtrate. It was taken up with methylene chloride, washed with ice water, $ a-

Dried 2o ', concentrated and the residue distilled. 165 g of dimethyl 3,4-dichlorophenylhydroxy malonate were obtained. Kp _n , = 154 - 5 8 ⁰ C.

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Example 62 Method 21

32.7 g of 3,4-Dichlorphenylglyoxylsäureamid were suspended in 100 ml of methylene chloride, treated with 0.2 ml of triethylamine and added dropwise 15 g of trimethylsilyl cyanide. The mixture was stirred for 1 hour at room temperature, concentrated and recrystallized from toluene. 41 g of 3,4-dichlorophenyltrimethylsilyloxymalonic acid amidonitrile were obtained. Mp 148-149 ° C.

Example 62a

5 g of the product were stirred in 25 ml of concentrated sulfuric acid for 1 hour at 25 ⁰ C; The solution was added to ice, filtered off with suction and washed neutral. It incurred 3.2 g of 3,4-Dichlorphenylhydroxymalonsäurediamid.

Example 63 Method 21

OH ₀

CN Nh ₂

29.8 g Phenylglyoxysäureamid were suspended in 30 ml of ethylene glycol dimethyl ether,. Added 0.5 ml of triethylamine and treated with 5.4 g of hydrogen cyanide. There was a homogeneous solution. After removal of the solvent Phenylhydroxymalonsäureamidnitril remained.

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Example A Plutella test

Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether

to prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into the preparation of active compound of the desired concentration and are populated with caterpillars of the cabbage (Plutella maculipennis) while the leaves are still moist.

After the desired time the kill is determined in%. 100% means that all caterpillars have been killed; 0% means that no caterpillars have been killed.

In this test, e.g. the following compounds of the Preparation Examples have superior efficacy over the prior art: 37, 38, 38a, 4, 39, 40, 5, 36, 3, 2, 41, 16, 10, 19a, 1, 47, 50, 48.

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Example B

Tetranychus test (resistant)

Solvent: 3 parts by weight of dimethylformamide Emulsifier: '1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound with the stated amount of solvent and the stated amount of emulsifier and the concentrate is diluted with water to the desired concentration.

Bean plants (Phaseolus vulgaris) which are heavily infested by all stages of development of the common spider mite or bean spider mite (Tetranychus urticae) are treated by being dipped into the preparation of active compound of the desired concentration.

After the desired time the kill is determined in%. 100.% means that all spider mites have been killed; 0% means that no spider mites have been killed.

In this test, e.g. the following compounds of preparation examples superior efficiency over the prior art: 37, 39, 40, 9, 5, 36, 41, 16, 10, 19a, 1, 47, 49, 50, 48.

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Example C

Test with Lucilia cuprina res. Larvae

Emulsifier: 35 parts by weight of ethylene glycol monomethyl ether 35 parts by weight of nonylphenol polyglycol ether

To produce a suitable preparation of active compound, three parts by weight of active compound are mixed with seven parts by weight of the abovementioned solvent mixture, and the concentrate thus obtained is diluted with water to the particular desired concentration.

Approximately 20 Lucilia cuprina res.-larvae are placed in a test tube containing about 1 cm ² horse meat and 0.5 ml of the active ingredient preparation. After 24 hours the mortality rate is determined.

In this test, e.g. the compound of Example (47) at a drug concentration of 1000 ppm a 100% kill.

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Example D

Limit concentration test / root systemic effect

Test Insect: Myzus pesicae Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the indicated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

The preparation of active compound is intimately mixed with soil. In this case, the concentration of the active substance in the preparation plays virtually no role, the only decisive factor is the weight of active substance per unit volume of soil, which is stated in ppm (= mg / l). Fill the treated soil in pots and plant them with cabbage (Brassica oleracea). The active ingredient can be absorbed by the plant roots from the soil and transported into the leaves.

For the proof of the root systemic effect, after 7 days only the leaves are covered with the above-mentioned test animals. After another 2 days, the evaluation is done by counting or estimating the dead animals. From the kill numbers, the root systemic effect of the drug is derived. She is 100%, if all

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Test animals are killed and O%, if just as many test insects live as in the untreated control.

In this test, e.g. the following compounds of the preparation examples superior effect over the prior art: 1, 13, 27, 33, 47, 52nd

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Example E ,

Limit concentration test / root systemic effect

Test Insect: Phaedon cochleariae Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the indicated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

The WirkstoffZubereitung is intimately mixed with soil. In this case, the concentration of the active substance in the preparation plays virtually no role, the only decisive factor is the weight of active substance per unit volume of soil, which is stated in ppm (= mg / l). Fill the treated soil in pots and plant them with cabbage (Brassica oleracea). The active ingredient can be absorbed by the plant roots from the soil and transported into the leaves.

For the detection of the root systemic effect, after 7 days exclusively the leaves are covered with the above-mentioned test animals. After another 2 days, the evaluation is carried out by counting or estimating the dead animals. From the mortality the root systemic effect of the active substance is derived. She is 100%, if all

Le A 22 012

Test animals are killed and O%, if just as many test insects live as in the untreated control.

In this test, e.g. the following compounds of Preparation Examples superior effect over the prior art: 49.

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Example F

Limit concentration test / soil insects

Test insect: Phorbia antiqua (in the soil) Solvent: 3 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the indicated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

The active ingredient preparation is intimately mixed with the soil. In this case, the concentration of the active ingredient in the preparation plays virtually no role, the only decisive factor is the amount of active ingredient per unit volume of soil, which is stated in ppm (= mg / l). The soil is poured into pots and allowed to stand at room temperature.

After 24 hours, the test animals are placed in the treated soil and after another 2 to 7 days, the efficiency of the active ingredient is determined by counting the dead and living test insects in%. The efficiency is 100%, if all test insects have been killed, it is 0%, if there are just as many test insects live as in the untreated control.

Le A 2 2 012

In this test, e.g. the following compounds of Preparation Examples superior effect over the prior art: 1, 47, 48, 40, 39, 35, 38a.

Le A 22 012

Claims (3)

20.9.1983 - 141 -. 62 918/11 brfindunqsaηspruch 1, pesticides, characterized by a content of substituted malonic acid derivatives of the general formula I. .2 v / if egg R is alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, aryl, heteroaryl, which may optionally be substituted, R is hydrogen, trialkylsilyl and also alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulfenyl, arylsulfenyl, alkylsulphonyl, arylsulphonyl, alkylaminosulphonyl, dialkylaminosulphonyl, arylamino * sulphonyl, arylalkylaminosulphonyl, which may optionally be substituted ssin, as well as radicals of the formula -CO-NR ⁵ R ⁶
stands, where R and R independently of one another represent hydrogen, alkyl, cycloalkyl, aryl, alkylaminocarbonyl, arylaminocarbonyl, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, alkylsulphonyl, arylsulphonyl, where these radicals may optionally be substituted, 20,9,1983 - 142 - 62 918/11 and R independently of one another represent the radicals amino, OX, where X is hydrogen, optionally substituted alkyl or cycloalkyl, aralkyl and also an equivalent alkali or alkaline earth metal, furthermore, R and R "'are alkylamino, arylamino, aralkylamines, dialkylamino, cycloalkylamino, alkenylamines, trialkylsilylamino, trialkylsilylalkylamino, nitrogen-containing saturated heterocyclic radicals which optionally contain further heteroatoms, where the radicals may optionally be substituted, furthermore R and R stand for radicals of the formula -NHR ⁷ , in which for hydroxyl, forayl, alkylcarbonyl, alkenylcarbonyl, cycloalkenylcarbonyl, arylcarbonyl, amino, alkylamino, arylamino, alkylarylamino, dialkylamino, aikylaminocarbonylamino (-NH-C-NH-alkyl), alkylaminothiocarbonylamino (-NH-C-NH-alkyl), arylaminocarbonylamino, arylaminothiocarbonylamino, 0
it Alkylcarbonylamino (-NH-C-alkyl), arylcarbonylamino, alkylsulfonylaminocarbonylamino (-NH-C-NHSO ₂ -alkyl), Arylsulfonylaminocarbonylamino, Aikylcarbonylaminocarbonylamino 0 0
η a (-NH-C-NH-C-alkyl), Arylcaroonylaminocaroonylamino, wherein the alkyl or aryl radicals given 20,9,1983 - 143 - 62 918/11 if they can be substituted, R and R " ¹ " are forner radicals of the formula -NH-N = C , in which R is alkyl or aryl, which may be optionally substituted, and R stands for hydrogen or alkyl » 2 * Use of substituted Malonsäuredsrivaten of formula I according to item I _1, characterized in that they are used for pest control » 2 ^ 4 If R stands for hydrogen, then R and R must not be amino in addition to extenders and / or surface-active agents. 3, a method for combating pests, characterized in that one carries out substituted malonic acid derivatives of the formula I according to item 1 on these and / or their habitat.