DE2918591A1 - NEW 4-SUBSTITUTED 5,6,7,8-TETRAHYDROCHINOLINE, THEIR PRODUCTION AND USE - Google Patents

Description

in the

R for hydrogen, for a straight chain or

branched alkyl radical with 1 to 12 carbon atoms, for a benzyl radical, for a phenyl radical, by one or two chlorine atoms or

can be substituted by trifluoromethyl or by an alkyl group with 1 to 4 carbon atoms, for alkoxycarbonyl with 1 to 6 carbon atoms, for arylaminocarbonyl, the aryl radical being substituted by halogen, -CF ₃ or alkyl with 1 to ά

Carbon atoms substituted ssin can, for N-alkyl-arylaminocarbonyl, the alkyl rst is one with 1 to 3 carbon atoms and the aryl group can be substituted by halogen, -CF "or alkyl having 1 to 4 carbon atoms

can, for aminocarbonyl, for alkylaminocarbonyl having 1 to 10 carbon atoms or for dialkylaminocarbonyl with 1 to 10 carbon atoms,

030047/0098

-Sg

HOE 79 / FB 09 (Ge. 604)

R is hydrogen, a straight-chain or branched one

th alkyl radical with 1 to 12 carbon atoms, a benzyl radical, a phenyl radical, which by one or two chlorine atoms, by trifluoromethyl or nitro or by alkyl with 1 to 4 carbons

substance atoms can be substituted, an alkoxycarbonyl radical with 1 to 6 carbon atoms, a phenylthio, morpholino or piperidino radical, an arylamino radical, including aryl

- Halogen or alkyl of 1 to 4 carbon

atoms can be substituted, means or

'

R and R together stand for -CH-CH-CH-CH «-,

R is hydrogen or an alkyl

has a remainder with 1 to 4 carbon atoms,

R is hydrogen, a straight-chain or branched one

Is an alkyl radical with 1 to 12 carbon atoms, 2Q

R represents hydrogen or an alkyl radical with 1 to

4 carbon atoms, and

R is hydrogen or an alkyl radical with 1 to 6

Carbon atoms is morbid

7 R ⁸

A for a residue -SR, a residue -N ^ r ⁹ ♦ ^one

Radical -S- (CH ₉ ) -OCN, or a radical 0

-N- (CH-) -0-CN _n with η = 2 or 3, H -. Υ "

7 9

where R to R, Y and Y ^{1 have} the following meanings:

0300A7 / 0098

HOE 79 / F B09 (Ge. 604)

R - a straight-chain or branched alkyl radical

with 1 to 12 carbon atoms, an arylmethyl

where the aryl radical
rest, γ by halogen or trifluoromethyl

may be substituted, a 2-furylmethyl radical, a Q-hydroxyethyl radical, a β- or / '- hydroxypropyl radical or a radical of the formulas -CH ₀ COOH, -CH (CH,) COOH, -CH ₀ CH

-CH CHCH _{0 0} OH, -CHCOOH, CH ₁₇ CO-, C ₀ H ₁ -CO-, & ι ί ·, j zo

OH CH ₂ COOH

CgHgCO-, a phenyl radical, replaced by hydroxy, nitro or alkyl having 1 to 4 carbon atoms or can be substituted by -COOH, or a cc- or 0-naphthyl radical or a cyclohexyl radical,

R = a phenyl radical, which is replaced by a or ζωβί halo

genatome, trifluoromethyl, nitro, one or two alkyl radicals8 with 1 to 4 carbon atoms, dimethylamino, -COOCH ₃ , -COOC H ₅ , 4'-chlorophenoxy, 2'-chlorophenoxy, 2 ', 4'-dichlorophenoxy, 4 ^f -phen-

oxy, methoxy or ethoxy may be substituted, a benzamido radical, a straight-chain or branched one Alkyl radical of the formulas

R ¹⁰ R ¹²

25 -CH. _ΛΛ or -CH ₀ CH. ." or

\ _R 11 Z \ _R 1 ^

-CH ₂ CH ₂ CH ₂ R ¹⁴ , where R ¹⁰ to R ^{14 have the} following meanings:

10

R = hydrogen, a 2-furyl radical, a ß-pyridino

rest, a phenyl radical that is replaced by a chlorine atom or an alkyl radical having 1 to 3 carbon atoms or a 3,4-dioxomethylene radical may be substituted, or a dialkylamino radical, where alkyl is each 1 to 5 carbons

substance atoms or a piperidyl or

0300A7 / 0098

HOE 79 / F BO9 (Ge. 604)

Morpholino or a bicyclo [2.2.2] heptyl radical or is a cyclohexyl radical,

R = hydrogen or methyl,

R ¹² = hydrogen or alkyl with 1 to 3 carbons

material atoms,

13th
R - phenyl, hydroxy, a dialkylamino radical with

10 - 1 to 5 carbon atoms each in the alkyl

chains, methoxy or hydroxyethylamino,

R - Dialkylamino, each with 1 to 5 carbon

atoms in the alkyl chains, alkoxy with 1 to 4

15 carbon atoms, hydroxy, morpholino, N-methyl-

piperazino, hydroxyethylamino or (^ ethylamino,

R = hydrogen or - but only in the case that

R is phenyl - a straight-chain or

20 ter alkyl radical with 1 to 5 carbon atoms or

is a hydroxyethyl radical, but also 9
R and R together for radicals of the formulas -N = CH-N = CH-,

-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ - or -CH ₂ CH ₂ N

-CH ₂ CH ₂ OCH ₂ CH ₂ -, -CHgCHgCHgCH

> the -CH ₂ CH ₂

Can stand CH _3,

Y = alkyl with 1 to 18 carbon atoms, phenyl, the through

C ₁ . to c -alkyl, -Cl, -CF "or -NO substituted

3 yrs

tuiert or benzo-fused, or cycloalkyl with 5 or 6 carbon atoms,

Y ¹ = hydrogen or, if Y for alkyl with 1 to 4

Carbon atoms, also with alkyl

up to 4 carbon atoms.

030047/00 98
ORIGINAL INSPECTED

HOE 79 / F 8 09 (Ge. 604)

Since the ring nitrogen atom in position 1 has basic properties has, the compounds can also be in the form of salts with inorganic or organic acids.

Examples of such salts are salts with inorganic acids, for example phosphates, phosphites, chlorides, bromides, dodides, sulfates and salts with organic mono- and polycarboxylic acids such as. B. acetates, laurates, citrates, tartrates, oxalates, benzoates, sulfonates or phosphonates.
10

/
Of the new compounds described by the formula (i)

7 ^ R ^ can be those in which A = -SR or -N _n g, in

R the lilise produce that one compounds of the formula (il)

(II),

R ⁶

in which R to R have the meaning given above, with the equimolar amount of a mercaptan of the general formula (III) bzu ;. the equimolar to double-equimolar amount of one Amine of the general formula (IV)

7 R-SH. HN ^ _g

(III) (IV)

7 8 9

with R, R and R as indicated above, in the presence or absence of an inert solvent at temperatures of 50 to 150 or 130 to 200 ^° C. to react, the hydrochlorides being formed first.

030047/0098

ORIGINAL INSPECTED

-A

HOE 7.9 / F 809 (Ge. 604)

Preference is given to working in an inert, non-polar solvent in which the halogen compound is initially introduced, whereupon the nucleophilic component is fed in at elevated temperatures. The addition of catalytic Plengen NH.Cl accelerates the reaction process. Suitable non-polar solvents are, for. B. aliphatic ^ hydrocarbons with boiling ranges up to 200 ⁰ C, toluene, xylene, dioxane and halogenated hydrocarbons such as chloroform, carbon tetrachloride, chlorobenzene or dichlorobenzene. Toluene and xylene are preferred. If appropriate, polar solvents such as acetonitrile, dimethylformamide or hexamethylphosphoric triamide - the latter two are preferred - can be used under the same conditions.

The reaction temperatures are from 50 to 200 ^° C. One sets with

a mercaptan, temperatures of 50 to 150 are preferred

⁶ ° C., if the reaction is carried out with an amine, the preferred temperature range is 130 to 200 ^° C.

As already mentioned, even without the use of a solvent, each work in the specified temperature range.

While implementing the
compounds with flercaptans if these are used in an equimolar amount, based on the chlorine compound, the equimolar to double-equimolar amount is used when the latter is reacted with amines. When using strongly basic amines, double the equimolar amount is always required.

The process products obtained as hydrochlorides can be converted into the free quinolines with stronger bases. Suitable bases for this are, for. B. organic tertiary bases such as triethylamine or pyridine and preferably inorganic bases such. B. Na ₃ CO ₃ , K ₂ CO ₃ , NaOH or KOH. The inorganic bases are preferably used for neutralization in polar solvents such as. B. dissolved alcohols are used.

0300A7 / 0098

ORIGINAL INSPECTED

HOE 79 / F 809 (Ga. 604)

When the chlorine compounds are reacted with amines, the Compounds according to the invention also as hydrochlorides or also mixed with amine hydrochlorides. From these hydrochlorides can by treating with strong bases, ujie z. B. NaOH or KOH, whereby these are preferably used in the alcoholic phase, but can also be used in aqueous solution, the amines are recovered.

For the preparation of such compounds of formula (i), in

where A = -S- (CH ₉ ) -0-CN ^ or -N- (CH ₉ ) -0-CN ^ with

^{Δ n} It Y (J * ^Π Il Y

0 ^M 0

η - 2 or 3, compounds of the formula (i) are assumed with

7 7

-SR, in which R is ß-hydroxyethyl, ß-hydroxypropyl or

h • RÖ

« -Hydroxypropyl or those in which A = -N g with R

8 U ^

s = H and R = β-hydroxyethyl, β-hydroxypropyl or α-hydroxypropyl is, from, and sets this with the equimolar amount of one Isocyanate of the general formula (V)

Y-N = C = O (V)

in which Y stands for alkyl with 1 to 18 carbon atoms or for a phenyl radical which _{can be substituted or benzofused by C ^ - to C. -alkyl, -Cl, -CF 3} or N0 "or for cycloalkyl with 5 or 6 C Atoms is in an inert solvent and in the presence of catalytic amounts of a base, or with the equivalent amount of a dialkylcarbamic acid chloride of the general formula (Vl)

Y.

N-C-Cl (VI)

30 ^Y 0

in which Y = Y 'and is alkyl having 1 to 4 carbon atoms, in an inert solvent and in the presence of equimolar amounts of an auxiliary base, in each case at 20 to 150 ^° C.

Q300A7 / 0098

ORIGINAL INSPECTED

HOE 79 / F 809 (Gs. 604)

The reaction with isocyanates Uird in the Ueise made by first together are the reactants in an inert solvent, then catalytic amounts of a base and adding thereto 1 to 4 hours at 20 to 150, preferably 40 to 140 ⁰ C -erwärmt.

Inert solvents are e.g. B. dioxane, toluene, xylene or acetonitrile or also CH ₂ Cl ₂ or CHCl ₃ .

Suitable basic catalysts are, for example, triethylamine or 1,4-diazabicyclo [2,2,2] octane; their amount is 5 * 10 to 5 * 10 "moles per mole of hydroxy compound to be reacted Isocyanate excess of up to about 10 mol $ can be advantageous in some cases.

If the reaction is carried out with a dialkylcarbamic acid chloride, the procedure is basically the same, but none is required Catalyst. It is necessary, however, that equimolar amounts of an auxiliary base are present.

Suitable auxiliary bases are organic tertiary bases, such as. B. triethylamine or pyridine, or inorganic bases, such as. B. Na ₀ CO ₁₇ or K _o C0 ". Here, too, an excess of acid chloride of up to about 10 mol- ^ can bring advantages. 25th

Suitable isocyanates are, for example, methyl isocyanate, ethyl isocyanate, Propyl isocyanate, butyl isocyanate, octadecyl isocyanate, phenyl isocyanate, cyclohexyl isocyanate, chlorophenyl isocyanate, Naphthyl isocyanate.

Dialkylcarbamic acid chlorides are e.g. B. named: Dimethylcarbamic acid chloride, Diethyl carbamic acid chloride, dipropyl carbamic acid chloride and diphenyl carbamic acid chloride.

030.0A7 / 0098

ORIGINAL INSPECTED

HOE 79 / Γ 809 (Gb. 604)

The compounds according to the invention are ζ. T. by recrystallization, ζ. T. purified by distillation, uobei the the latter case applies in particular if ωβηη is Uer-

r8 9 bonds in which A = -N ^ g with R = alkyl.

These substances exist as colorless to yellow, viscous oils.

The starting material for the production of 5,6,7,8-tetrahydroquinolines of the formula (i) required 4-chloro-5,6,7,8-tetrahydroquinolines the formula (il) can analogously to the method of

E. -Ochiai, Fl. Takahashi and R. Tanabe, Chem. Pharm. Bull. Soc. Oap. 15 (9), 1385 (1967), the 2-pethyl-4-oxy-5,6,7,8-tetrahydroquinolines with POC1 "to implement, to be represented. Called are for example: 4-chloro-2-methyl-5,6,7,8-tetrahydroquinoline, 4-chloro-tetrahydroquinoline, 4-chloro-2-methyl-6-isopropyl-5,6,7,8-tetrahydroquinoline, 4-ChloΓ-2-n-propyl-8-isopropyl-5,6,7,8-tetrahydroquinoline, 4-chloro-2,6-dimethyl-5,6,7,8-tetrahydroquinoline, 9-chloro-1,2,3,4,5,6,7,8-octahydroacridine, 3,4-dichloro-2-methyl-5,6,7,8-tetrahydroquinoline, 4-chloro-2,8-dimethyl-5,6,7,8-tetrahydroquinoline, 4-chloro-3,6-dimethyl-5,6,7,8-tetrahydroquinolinyl-2-carboxylic acid methyl ester.

Mercaptans suitable for reaction with the chlorine compounds are, for example, thiophenol, 2-furyl methanethiol, 2-thioglycerol, 4-chlorobenzyl mercaptan, thiosuccinic acid, thioacetic acid, Thiopropionic acid, benzyl mercaptan, pentachlorothiophenol, p-hydroxythiophenol, p-chlorothiophenol, p-bromothiophenol, p-methylthiophenol, p-l \ litrothiophenol, 2-wercaptonaphthalene, thioglycol, Thioacetic acid ester, thiobenzoic acid, 2-MeTCaPtObBnZOee acid, 4-bromo-3-methylthiophenol, 4-boom-2-methylthiophenol, Mercaptoacetic acid, 2,4,5-trichlorothiqphenol, 2- and 3-mercaptopropionic acid.

Suitable amines for reaction with the chlorine compounds are, for. B. named: 3-dimethylaminopropylamine, 3,4- and 3,5-dichloroaniline, N-methylaniline, 3-bromoaniline, 3-trifluoromethylaniline, 2,6-diisopropylaniline, 4-chlorobenzylamine, benzhydrazide,

Q300A7 / 0098

ty ~ ^: -2318591

-X-

HOE 79 / F 809 (Gs. 604)

1,2,4-triazole, 0-hydroxyethylamine, ß-hydroxypropylamine, j'-hydroxypropylamine, N-ethyl-3-toluidine, N-propylaniline, N-ButyiLaniline, N-Benzylaniline, o * -Flethoxy-propylamine, </ * - Isopropoxy-propylamine, i-Fethyl-i-cyclohexylamine, bicyclo- (2,2,1) -hBpt (2) yl-methylamine, / -Morpholinopropylamine, ß-phenylethylamine, α-phenylethylamine, 2-furyl-methylamine, exo- (2) -norbornylamine, 2,6-dimethylaniline, 2- and 4-isopropylaniline, 2,3- or 4-chloroaniline, 4-fluoroaniline, 4-n-butylaniline, naphthylamine and cyclooctylamine.

10 ι

The substances of the general formula (i) according to the invention are preferably suitable as biocides. They have a relatively broad effect against fungi, bacteria and algae. Particularly ineffective are they against phytopathogenic fungi such as B. Powdery mildew,

15 Botrytis cinerea, rust fungi, Cercospora betae, Cladosporium

fulvum, Fusicladium dendriticum, and Rhizoctonia solani. An excellent one They also show activity against the Oomycetes belonging to the class of Phycomycetes such as z. B. Phytophthora, Peronospora, Pseudoperonospora, Plasmopara and Phythium.

The compounds are also effective against phytopathogenic bacteria z. B. Xanthomonas phaseoli, Xanthomonas oryzae, Xanthomonas citri, Xanthomonas malvacearum, Eruinia carotovora and Corynebacterium michiganense good and effective.

Also against non-phytopathogenic fungi and bacteria that are on If technical substrates grow and these degrade or destroy, the compounds can be used with excellent effect will. So they record, inter alia. Aureobasidium pullulans, Ulocladium consortiale, Aspergillus niger, Penicillium funiculosum, Poria monticola and Coniophora puteana. So do the bacteria Escherichia coli, Bacillus subtilis and Aerobacter aerogenes inhibited in their growth by the claimed compounds. The compounds are ultimately also against various algae

35 types uie z. B. Chlorella vulgaris, Anabaena flos-aquae, Spirogyro spp. and Enteromorpha spp. effective.

030047/0098

ORIGINAL INSPECTED

HOE 79 / F 809 (Ge. 604)

The agents can be formulated in the usual way as dusts, wettable powders, dispersions or emulsion concentrates. The content of the total active ingredient is preferably 10 to 90 %. In addition, the formulations contain the customary adhesives, wetting agents, dispersants, fillers and carriers.

The invention is to be further illustrated by the following examples.

10 Example 1 4-Phenylthio-2-methyl-5,6,7,8-tetrahydroquinoline

0.2 PLOL (36.3 g) of 4-chloro-2-methyl-5,6,7,8-tetrahydroquinoline uerden with 0.2 mole (22 g) of thiophenol was added and heated up to 120 ⁰ C. The mixture is allowed to react with stirring, cooled, taken up in 100 ml of toluene and 0.2 mol (20 g) of triethylamine is added dropwise. After stirring for one hour, the triethylamine hydrochloride is filtered off with suction and the mother liquor is evaporated in vacuo. The residue is rubbed with ice, whereupon it crystallizes. 27 g of product are recrystallized from η-hexane - melting point: 116 ^° C.

Example 2 25 4- (2 ^f -Furylmethylthio) -2-methyl-5,6,7,8-tetrahydroquinoline

0.2 mol (36.3 g) of 4-chloro-2-tnethyl-5,6,7,8-tetrahydroquinoline and 0.2 mole (23 g) of 2-Furylmethanthiol are combined and heated to 140 to 150 ⁰ C. It is allowed to react, cooled and taken up in 100 ml of toluene and 0.2 mol (20 g) of triethylamine. After stirring for one hour, the salt is filtered and the mother liquor is concentrated. After recrystallization from heptane, 21.4 g of product with a melting point of 91 ° C. are obtained.

030047/0098

HOE 79 / F 809 (Ge. 604) Example 3

4- (2 *, 3'-dihydroxy-1'-propylthio) -2-methyl-5,6,7,8-tetrahydroquinoline hydrochloride
.

36.3 g (0.2 mol) of 4-chloro-2-methyl-5,6,7,8-tetrahydroquinoline uerden added dropwise 140 ⁰ C to siner solution of 21.9 g of 2-thioglycerol in 100 ml of xylene bsi, uobei after some time a u / icer precipitate forms, which is sucked off. The yield is 38.0 g of 10 des; Product of melting point 204 ⁰ C. C ₁₃ H ₂₀ ClNO ₂ S - PIG: 289.5

C calc .: 53.9 H calc .: 6.9 N calc .: 4.8 found: 53.6 found: 6.9 found: 4.6

The free base is obtained by dissolving 27.5 g of the hydrochloride in approx. 100 ml of methanol and neutralizing it with an equimolar amount of sodium hydroxide solution. 22 g of product with a melting point of 159 ^° C. are obtained. C ₁₃ H ₁₉ NO ₂ S - MW: 253

C bar .: 61.7 H calc .: 7.5 N calc .: 5.5 found: 61.6 found: 7.7 found: 5.5

Example 4
4- (4'-chlorobenzylthio) -2-methyl-5,6,7,8-tetrahydroquinoline

36.3 g of 4-chloro-2-methyl-5,6,7,8-tetrahydroquinoline are added dropwise at 140 ° C. to a solution of 34 g (0.2 mol) of 4-chlorobenzyl mercaptan in 100 ml of xylene, after a while time the hydro-chloride 30 This arises u / ill be sucked out and neutralized in 20 ml of methanol with an equimolar amount of sodium hydroxide to give 16.5 g of product of melting point 131 ⁰ C. C ₁₇ H ₁₈ CLN - MG.:. 303.5

C calc .: 67.2 H calc .: 5.9 N calc .: 4.6 found: 66.8 found: 6.0 found: 4.5

In analogy, the following were produced:

0300A7 / 0098

ORIGINAL INSPECTED

σ co ο

3sp. Connection, yield Melting point
(T) 5 4- (2-methyl-5,6,7,8-tetrahydroquinolinyl) thiobernstainic acid 54 240 6th 4- (2-MBthy1-5,6,7,8-tetrahydroquinolinyl) -thioacetic acid hydrochloride 87 256 7th 4-Benzylthio-2-methyl-5,6,7,8-tatrahydroquinoline 32 109 β 4-pentachlorophenylthio-2-mathyl-5,6,7,8-tetrahydroquinoline 53 176 9 4- (4'-hydroxyphenylthio) -2-methyl-5,6,7,8-tatrahydroquinoline 47 128 10 4- (4'-Bromophanylthio) -2-methyl-5,6,7,8-tetrahydroquinoline 49 180-5 11 4- (4'-methylphenylthio) -2-methyl-5,6,7,8-tetrahydroquinoline 28 95-7 12th 4- (3 ', 4 ^f , 5', 6 "-Tetrahydropyriniidino-2 ^l -) thio-2-methyl-5,6,7,8-
tetrahydroquinoline hydrochloride 22nd 171-4 13th 4- (4 ^l -nitrophenylthio) -2-methyl-5,6,7,8-tetrahydroquinoline-
hydrochloride 34 232 14th 4- (4'-nitrophenylthio) -2-methyl-5 _t 6,7,8-tetrahydroquinoline 21st 130-2 15th 4- (4 ^L -chlorophenylthio) -2-methyl-5,6,7,8-tetrahydroquinoline 40 121 16 4- (2'-f \ laphthylthio) -2-methyl-5,6,7,8-tetrahydroquinoline 86 95-6 17th 4- (2-MBthyl-5,6,7,8-tetrahydroquinolinyl) -thio-3'-propion-
acid hydrochloride 52 228 18th 4- (2-methyl-5,6 _> 7,8-tetrahydroquinolinyl) -thio-2'-propion-
acid hydrochloride 82 110

too cn

co 00

E.g. Link ""' yield
(%) Melting point
, ( ⁰ C) 19th 4- (2'-Hydroxyethylthio) -2-methy1-5,6,7,8-tetrahydroquinoline-
hydrochloride 61 188 20th 4- (2'-Hydroxyethylthio) -2-methyl-5,6,7,8-tetrahydroquinoline 81 103-4 21st 4- (2-MBthyl-5,6,7,8-tatrahydroquinolinyl) -thio-acetic acid-
methyl ester hydrochloride 64 200 22nd 4- (2-l ^v lethyl-5,6,7,8-tetrahydrqchinolinyl) thio-2'-benzoate
hydrochloride 92 228 23 4-Benzoylthio-2-methyl-5,6,7,8-tBtΓahydΓoquinoline hydrochloride 70 from 210 dec. 24 4- (4'-bromo-3 ^l -methyiphenylthio) -2-methyl-5,6,7,8-tetrahydro-
quinoline hydrochloride 92 from 246 dec. 25th 4-Acetylthio-2- methyl-5,6,7,8-tetrahydroquinoline 61 115 26th 4- (2 ^l -thiazolinyl-thio) -2-methyl-5,6,7,8-tetrahydroquinoline-
hydrochloride 22nd 297 dec. 27 4- (2, 4, 5'-trichlorophenylthio) -2-methyl-5,6,7,8-tetrahydro-
quinoline 76 114 28 4-propionylthio-2-methyl-5,6,7,8-tetrahydroquinoline 67 114 29 4- (2-riethyl-5,6,7,8-tetrahydroquinolinyl) -thio-2'-benzoic acid 33 204 30th 4-Benzoylthio-2-methyl-5,6,7,8-tetrahydroquinoline 68 75 31 4- (3'-MBthyl-4'-bromophehylthio) -2-methyl-5,6,7,8-tetrahydro-
quinoline 94 77

co α

(73

cn co

Currently

■ HOE 79 / F 809 (Ge. 604) example 32

4_ (3 "_0imethylaminopropyl-1'-amino) -2-methyl-5,6,7,8-tetrahydroquinoline
5

61.2 g (0.6 MoI) 3-Oimathylaminopropylamin and 72.6 g of 4-chloro-2-methyl-5,6,7,8-tetrahydroquinoline and catalytic amounts NH.Cl are kept for 15 hours at 160 ⁰ C. It is cooled, taken up in 100 ml of methanol and neutralized with an equimolar amount of sodium hydroxide solution. The reaction mixture obtained in this way is brought to dryness in vacuo and the free base is extracted with chloroform. The chloroform solution is with Na ₂ SO. dried and, after filtration, spun off in vacuo. The remaining oil yields 86.6 g of product after vacuum distillation at 160 ^° CO, 2 mbar.

^C 15 ^H 25 ^N 3 - MG : 247 H 10, 1 N 17 , 0 C calc .: 72, 9 10, 3 16 found: 72, 4th example 33

4- (3 ', 4'-dichloroanilino) -2-methyl-5,6,7,8-tetrahydroquinoline

54.3 g (0.3 mol) of 4-chloro-2-methyl-5,6,7, S-tetrahydroquinoline and 72.9 g (0.45 mol) of 3,4-dichloroaniline and catalytic amounts of NHXl are 12 hours heated to 160 to 170 ^{° C.} After this time the contents of the flask have solidified, they are cooled and taken up in 100 ml of methanol. It is then neutralized with the equimolar amount of sodium hydroxide solution and the reaction mixture is digested with water. The product is filtered and dried in vacuo. The Ausbsute is approximately 61.6 g of melting point 170 ⁰ C. The compound was recrystallized from CCl.

30 047/0098

HOE 79 / F 8Q9 (Gs. 604)

^C 16 ^H 16 ^C1 2 ^N 2 - " ^{G: 307}

C calc .: 62.5 H calc .: 5.2 N bar .: 9.1

found: 62.5 found: 5.2 gaf .: 8.9

5. · ■

Example 34

4-CN-l ^v lethylanilino) -2-5,6,7,8-tetrahydroquinoline-mBthyl

36.3 g (0.2%) of 4-chloro-tetrahydroquinoline and 21.5 g (0.2 mol) of N-methylaniline and catalytic amounts of NH ^ Cl are heated to 180 "G for 4 hours. / Cools down and adds 100 ml of methanol are added. Then it is neutralized with the equimolar amount of sodium hydroxide solution. The solvent is drawn off on a rotary evaporator, taken up in chloroform, the solution is dried with Na ₃ SO 3 and filtered. The chloroform is evaporated and the residue is distilled in a high vacuum at 136 up to 138 ° (/ Q, 13 mbar. The yield is 34.5 g. C ₁₇ H ₂₀ N ₂ - MW: 252

20 C calc. 81.0 H calc .: 7.9 N calc .: 11.1 found: 80.8 found: 8.0 found: 11.3

Example 35

25 4- (3 ^l ~ chloroanilino) -2-methyl-6-isopropyl-5,6,7,8-tetrahydroquinoline

22.3 g (0.1 mol) of 4-chloro-2-methyl-6-isopropyl-5,6,7,8-tetrahydroquinoline and 12.8 g (0.1 mol) of 3-chloroaniline and catalytic amounts of NH. C1 are kept at 160 to 176 ^° C. for 3 hours. The mass becomes tough. It is cooled, taken up in 100 ml of methanol and then the equimolar amount of sodium hydroxide solution is added. It is evaporated in a vacuum, taken up in chloroform and the solution is dried _{with Na 3} SO _4. It is filtered, the chloroform is evaporated and the

35 installed from CCl. around. 10 g of product of melting point 164 ⁰ C

030047/0098

ORIGINAL INSPECTED

HOE 79 / F 8 09 (Gb. 604)

- MG: 314.5

C calc .: 72.5 H calc .: 7.3 N calc .: 8.9

found: 73.1 found: 7.2 found: 8.9

Example 36

4- (3 ', 4'-dichloroanilino) -2-n-propyl-8-isopropyl-5,6,7,8-tetrahydroquinoline

25.15 g (0.1 mol) of 4-chloro-2-n-propyl-8-isopropyl-5,6,7,8-tetrahydroquinoline and 16.2 g (0.1 mol) of 3,4-dichloroaniline soup catalytic amounts of NH.C1 u / earth ^{kept at 160 to 170 0} C for 7 hours. The viscous mass is dissolved in 100 ml of methanol and an equimolar amount of 0.1 molar sodium hydroxide solution is added. It is concentrated to dryness and taken up in chloroform. The solution is treated with NaS0. dried and filtered. The filtrate is spun off and the residue from CCl. recrystallized. This gives 27 g of product with a melting point of 111 ^° C.

20 ^C 21 ^H 26 ^C1 2 ^N 2 ^{-MGi 377}

C calc .: 66.8 H calc .: 6.9 N calc .: 7.4 found: 66.9 found: 7.0 found: 7.5

25 Example 37

4- (3'-trifluoromethylanilino) -2,6-dimethyl-5,6,7,8-tetrahydroquinoline

15.6 g (0.08 mol) of 4-chloro-2,6-dimethyl-5,6,7,8-tetrahydroquinoline, 12.9 g (0.08 mol) of 3-trifluoromethylaniline and catalytic amounts of NH.C1 merden heated to 175 ^{° C.} The mass becomes tough and finally solid. It is worked up as described in Example 36 and the product is crystallized from CCl. 11.5 g product uom

35 melting point 131 ⁰ C.

Q300A7 / 0098

HOE 79 / F 809 (Gb. 604)

Example 38

17.4 g (0.1 PIoI) 9-chloro-1,2,3,4,5,6,7,8-octahydroacridine, 13 g 3,4-dichloroaniline and catalytic amounts of NH., Cl are for 7 hours 180 ⁰ C held. The solid formed on cooling is worked up as described in Example 36 and the product is obtained from CCl. recrystallized. 10.2 g of product with a melting point of 102 ^° C.

^{10 C} 19 ^H 20 ^Cl 2 ^N 2 - ^{"Gi 34 _3?}

Example 39

4- (3 ^l , 4 ^f -Dichloroanilino) -3-chloro-2-methyl-5,6 _J 7,8-tetrahydro-15 quinoline

21.6 g (0.1 mole) Sj ^
16.2 g (0.1 mol) of 3,4-Oichloranilin and catalytic amounts NH ^ Cl Bierden 4 hours at 180 to 185 ⁰ C maintained. The mass becomes solid. It is worked up as described in Example 36 and the product from CCl. recrystallized. 33.2 g of product worn melting point 123 ⁰ C.

Example 40 25

4- (2 ', 6'-diisopropylanilino) -2,8-dimethyl-5,6,7,8-tetrahydroquinoline

19.6 g (0.1 mol) of 4-chloro-2, e-dimethyl-Sjö ^ ja-tetrahydroquinoline, 11.7 g (0.1 mol) of 2,6-diisopropylaniline and catalytic amounts of NH ^ Cl are 8 hours heated to 190 ^{0 C.} The cooled and solidified mass is worked up as in Example 36 and distilled in a high vacuum. 16. g of product are obtained at 190 ° C./0.07 mbar.

030047/0098

ORIGINAL INSPECTED

HOE 79 / F 8 09 (Gs. 604)

Example 41

4- (4 '- "Chlorobenzylamino) -3,6-dimethyl-5,6,7,8-tetrahydroquinolinyl-2-carboxylic acid methyl ester
5

25.35 g (0.1 mol) of 4-chloro-3,6-dimethyl-5,6,7,8-tetrahydroquinolinyl-2-carboxylic acid methyl ester, 18.4 g (0.13 mol) of 4-chlorobenzylamine and catalytic amounts NH.Cl be maintained for about 17 hours at 165 to 170 ⁰ C. It is worked up as described in Example 36 and the residue is distilled in a high vacuum. 8.5 g of product are obtained at 190 to 200 ° C./0.24 mbar. O ₂ MW: 358.5

C bar .: 66.9 H bar .: 6.4 N calc .: 7.8 15 found: 67.8 found: 6.6 found: 8.2

Example 42

4-N- (N'-Benzoylhydroazino) -2-methy1-5,6,7,8-tetrahydroquinoline hydrochloride

36.3 g (0.2 mol) of 4-chloro-2-methyl-5,6,7,8-tetrahydroquinoline, 27.3 g (0.2 mol) of benzhydrazide and catalytic amounts NH.Cl be at 135 ⁰ C stirred until the reaction starts. It is cooled and digested with acetone. 53.7 g of product uom mp 312 ⁰ C.

O - MG: 317.5

C calc .: 64.3 H calc .: 6.0 N calc .: 13.2 30 found: 64.0 found: 5.9 found: 13.3

030047/0098

HOE 79 / F 809 (Ge. 604) Example 43
4-triazolo-2-methyl-5,6,7,8-tetrahydroquinoline

36.3 g (0.2 mol) of 4-chloro-2-methyl-5,6,7,8-tstrahydroquinoline, 14 g (0.2 mol) of 1,2,4-triazole and catalytic amounts of NH.Cl are used Heated to 160 ^° C. for half an hour. It is allowed to cool, taken up in 100 ml of ethanol and an equimolar amount of sodium hydroxide solution is added. It is spun off in vacuo and then taken up in chloroform. After filtration, the chloroform is evaporated. 26.2 g of an oil which soon solidifies and has a melting point of 69 to 75 ^° C.

^C 12 ^H 14 ^N 4 - ^{mt 214}
Preparations were carried out analogously to Examples 32 to 41.

0300A7 / 0098

ORIGINAL INSPECTED

3sp,

link

co m 3

44 4- (3'Diethylaminopropyl-1'-amino) -2-methyl-5,6,7,8-tstrahydroquinoline

45 4- (2'-Diethylaminoethyl-1'-amino) -2-methyl-5,6,7,8-tetrahydroquinoline

46 4- (2'-dimethylaminoethyl-1 ^l amino) -2-methyl-5,6,7,8-tetrahydrochinolinohydrochlorid

47 4- (2'-Hydroxyethyl-1'-amino) -2-methyl-5,6,7,8-tetrahydroquinoline

48 4- (4'-Chloroanilino) -2-methyl-5,6,7,8-tetrahydroquinoline

49 4- (Cyclooctylamino) -2-methyl-5,6,7,8-tetrahydroquinoline

50 4- (Cyclohexylmethylamino) -2-methyl-5,6,7,8-tetrahydroquinoline

51 4- (4'-Tertiary-butylcyclohexyl-1'-amino) -2-methyl-5,6,7,8-tetrahydroquinoline

52 4- (4'-Chlorobenzylamino) -2-methyl-5,6,7,8-tetrahydroquinoline

53 4- (4'-Cyanobenzylamino) -2-methyl-5,6,7,8-tetrahydroquinoline

54 4- (N-Ethy1-3 • -methylanilino) -2-methy1-5,6,7,8-tetrahydroquinoline

55 4- (1- butylanilino) -2-methyl-5,6,7,8-tetrahydroquinoline

56 4- (N-propylanilino) -2-methyl-5,6,7,8-tetrahydroquinoline

57 4- (3 ^l -l ^v ) ethoxypropyl-1. -Amino) -2wmsthyl-5,6,7,8-tetrahydroquinoline

58 4- (3'-IsOPrOpOXyPrOPyI-I'-amino) -2-methyl-5,6,7,8-tetrahydroquinoline

59 4- (i'-Methyl-1'-cyclohexylatnino) -2-methyl-5,6,7,8-tetrahydroquinoline

60 4- [Bicyclo- (2,2,1) -hept-2 ^f -yl-methylamino] -2-methyl-5,6,7,8-tetrahydroquinoline Yield

64 78 48

93 32 49 69 11

68 88 61 92 59

53 76 86 78

Boiling point or melting point (° c)

170 / 0.65 mbar 160-165 / 0.2 mbar 279

154-6 153-4

84

85 185 / 0.65 mbar

179 130

152-7 / 0.53 mbar oil

157-160 / 0.53 mbar

151 / 0.13 mbar 160 / 0.13 mbar

65-70

90

u> O O

O O co 00

3sp. link
. ■ ■■ - j- yield
{%) Boiling point or
Melting point (° c) 61 4- (3'-hydroxypropyl-1'-amino) -2-methyl-5,6,7,8-tetrahydroquinoline 30th 149 62 4 -. (3 ^L -morpholinopropyl-1 '-atnino) -2-methyl-5,6,7,8-tetrahydroquinoline 73 187 / 0.065 mbar 63 4- (2'-methoxyethyl-I'-amino) -2-methyl-5,6,7,8-tetrahydroquinoline 71 130-136 / 0.13
mbar 64 4- (2-phenylethyl-1'-amino) -2-methyl-5,6,7,8-tetrahydroquinoline 70 112-13 65 4- (i'-phenylethyl-1'-amino) -2-methyl-5,6,7,8-tetrahydroquinoline 72 94-8 66 4- (Furfuryl-2 ^l -amino) -2-methyl-5,6,7,8-tetrahydroquinoline 72 115 67 4- (N'-Hydroxyethylamino-3'-propyl-1'-amino) -2-methyl-5,6,7,8-
tetrahydroquinoline 81 200-5 / 0.4 mbar 68 4- (N ^t -hydroxyethylamino-2 ^l -ethyl-1'-amino) -2-methyl-5,6,7,8-
tetrahydroquinoline 76 190-200 / 0.8
mbar 69 4- (N-Ethylanilino) -2-methyl ~ 5,6,7,8-tetrahydroquinoline 17th 144-5 70 4- (piperidyl-4 ¹ -methylamino) -2-methyl-5,6,7,8-tetrahydroquinoline-
hydrochloride 15th 337 71 4- (3'-l ^v ethylaminopropyl-1'-amino) -2-methyl-5,6,7,8-t et rahydro-
quinoline hydrochloride 83 oil 72 4- (3 ', 5 ^L -Dichloroanilino) -2-methyl-5,6,7,8-tetrahydroquinoline 54 195 73 4- (3 ^L -chloroanilino) -2-methyl-5,6,7,8-tetrahydroquinoline 72 193-5 74 4- (3 ^L -trifluoromethylanilino) -2-methyl-5,6,7,8-tetrahydroquinoline 84 136-8 75 4- (4 ^L - ( ^Y lethoxyanilino) -2-methyl-5,6,7,8-tetrahydroquinoline 41 135 76 4- (N-Benzylanilino) -2-methyl-5,6,7,8-tetrahydroquinoline 31 164-170 / 0.8
mbar 77. 4- (2 ', 6'-dimethylanilino) -2-methyl-5,6,7,8-tetrahydroquinoline 60 157-161

rc CD C.
• Ό, - ^. ■ η
0? 00 ο cn co tn ω
• cn α ^; ■ '

link

4- (2'-Isopropylanilino) -2-methyl-5,6,7,8-tetrahydroquinoline 4- (4'-Ethoxycarbonylphenylamino) -2-methyl-5,6,7,8-tetrahydroquinoline hydrochloride 4- (4'- Isopropylanilino) -2-methyl-5,6,7,8-tetrahydroquinoline 4- [4 ^l - (2 ^ll , 4 "-Dichlorophenoxy) anilino] -2-methyl-5,6,7,8-tetrahydroquinoline

4- (2 ^l -l ^v lBthyl-5 ^l -chloro-anilino) -2-methyl-5,6,7,8-tetrahydroquinoline

4- (2'-Rethyl-4'-chloroanilino) -2-methyl-5,6,7,8-tetrahydroquinoline 4- (Exo-2'-norbornylamino-2-methyl-5,6,7,8-tetrahydroquinoline 4- (3 ^l -Flethylanilino) -2-methyl-5,6,7,8-tetrahydro-4- (4'-l ^v lethylanilino) -2-methyl-5,6,7,8-tetrahydro-4- (3 ', 4'-Dimethoxyphenylsthyl-1 "-amino) -2-methyl-5,6,7,8-tetrahydroquinoline hydrochloride 4- (4'-Isopropylanilino) -2-n-propyl-8-isopropyl-5,6,7 , 8-tetrahydroquinoline

4- (2'-Isopropylanilino) -2-n-propyl-8-isopropyl-5,6,7,8-t-trahydroquinoline

4- (3'-trifluoromethylanilino) -2-n-propyl-8-isopropyl-5,6,7,8-tetrahydroquinoline

4- (3'-chloroanilino) -2-n-propyl-8-isopropyl-5,6,7,8-tetrahydroquinoline 4- (l \ ll ^v ethylanilino) -2-n-propyl-8-isopropyl-5, 6,7,8-tetrahydroquinoline 4- (4'-isopropylanilino) -2-methyl-6-isopropyl-5,6,7,8-t-trahydroquinoline

yield Boiling point or
Melting point ( ⁰ C) 81 157-159 81 sinters from 70 91 140-2 97 128-131 98 220-230 68 241-3 50 82 92 172-6 94 156-8 80 178 74 193-5 /
0.04 mbar 63 195-210 /
0.13 mbar 94 97 63 185-192 /
0.13 mbar 70 150-5 /
0.065 mbar 68 158

σ co ο

O O CO 00

3sp. link yield
(*) Boiling point or
Melting point ^) 94 4- (1- propylanilino) -2-methyl-6-isopropyl-5,6,7,8-tetrahydroquinoline 66 ' 140-155 /
0.065 mbar 95 4- (3 ', 4'-dichloroanilino) -2-methyl-6-isopropyl-5,6,7,8-tetrahydro
quinoline 68 188 96 4- (2 • -l ^y lethyl-4 ^l -chloroanilino) -2-yn-ethyl-6-isopropyl-5,6,7,8-tetra-
hydroquinoline 68 ■ 208 97 4- (2 ', 6'-dimethylanilino) -2-methyl-6-isopropyl-5,6,7,8-tetra-
hydroquinoline 72 158 98 4- (i'-MethylcyclohexyX-1'-mBthylatnino) -2-methyl-6-isopropyl-
5,6,7,8-tetrahydroquinoline 64 170-182 /
0.065 mbar 99 4- (3 ^l , 4 ^l -Dichloroanilino) -2,6-dimBthyl-5,6,7,8-tetrahydroquinoline 54 153 100 4- (2'-Ethylanilino) -2,6-dimethy1-5,6,7,8-tetrahydroquinoline 13th 135-7 101 4- (1- butylanilino) -2,6-dimethyl-5,6,7,8-tetrahydroquinoline 32 153-160 /
0.13 mbar 102 9- [bicyclo- (2,2,2) -heptyl-2'-exo-methylaminoj-i, 2,3,4,5,6,7,8-
octahydroacridine 27 170-200 /
0.065 mbar 103 4- (3 ', 4' -DichloraniNo) -2,3-dimethyl-5,6,7,8-tetrahydroquinoline 65 98 104 4- (3 ', 5'-dichloroanilino) -2,3-dimethyl-5,6,7,8-tetrahydroquinoline 70 99 105 4- (3'-TrifluoroniBthylanilino) -2-methyl-3-chloro-5,6,7,8-tetra-
hydroquinoline 50 56 106 4- (2 ', 6'-dimethylanilino) -2-methyl-3-chloro-5,6,7,8-tetrahydro
quinoline 30th 208 / 0.27 mbar

Π)

C3

'■ 9

IN CT

öS ¹ ο

co

E.g. Link yield
W. Boiling point or
Melting point ( ⁰ C) 107 4- (3 ^f , 4 ^t -Dichloroanilino) -2,8-dimethyl-5,6,7,8-tetrahydroquinoline 67 195-.210 /
0.2 mbar 108 4- (3 ^L -chloroanilino) -2,8-dimethyl-5,6,7,8-tetrahydroquinoline 63 152 109 4- (4'-Isopropylanilina) -2,8-dimethyl-5,6,7,8-tetrahydroquinoline 18th 134 110 4- [Bicyclo- (2,2,1) -heptyl-2'-exo-methylamino] -2, B-dimethyl-
5,6,7,8-tetrahydroquinoline 32 161 / 0.065 mbar 111 4- (4 ^L -n-butylanilino) -2,8-dimethyl-5,6,7,8-tetrahydroquinoline 81 214 / 0.065 mbar 112 4- (2 ', 6'-dimethylanilino) -2,8-dimethyl-5,6,7,8-tetrahydroquinoline 40 146 113 4- (3'-trifluoro (methylanilino) -2,8-dimethyl-5,6,7,8-tetrahydroquinoline 86 118 114 4- (3 ^l -trifluoromethylanilino) -3,6-dimethyl-2- (5,6,7,8-tatrahydro) -
quinolinylcarboxylic acid mathylaster 10 149 115 4- (4 ^l -Isopropylanilino) -3,6-dimethyl-2- (5,6,7,8-tetrahydro) -
quinolinylcarboxylic acid methyl ester 26th 152 116 4- (4 ^l -chlorobenzylamino) -3,6-dimethyl-2- (5,6,7,8-tetrahydro) -
quinolinylcarboxylic acid methyl ester 27 200-6 / 0.24 mbar 117 4- (i \ l-riethylanilino) -3,6-dimethyl-2 - (5,6,7,8-tetrahydro) -quinolinyl-
carboxylic acid methyl ester 15th 253 / 0.2 mbar 118 4- (4 ^L -Isopropylanilino) -2-phenyl-5,6,7,8-tetrahydroquinoline 87 158 119 4- (4'-Chlorophenylthio) -2-phenyl-5,6,7,8-tetrahydroquinoline 98 84 120 4- (4 ^l -Isopropylanilino) -2-methyl-3-morpholino-5,6,7,8-tetrahydro-
quinoline 84 oil 121 4- (4 ^L -Isopropylanilino) -3-phenyl-5,6,7,8-tetrahydroquinoline 69 147 122 4- (4'-Bromophenylthio) -3-phBnyl-5,6,7,8-t6trahydroquinoline 74 131 123 4- (2'-furfurylmethylthio) -3-phenyl-5,6,7,8-tetrahydroquinoline 52 58

σ m

UD CO

-26-

HOE 79 / F 8 09 (Gb. 604)

Example 124

4- (Octadecylcarbamoyloxyethylamino) -2-methy1-5,6,7,8-tetrahydroquinoline 5

20.7 g (0.1 mol) 4- (hydroxyethylamino) -2-methyl-5,6,7,8-tetrahydroquinoline and 29.5 g octadecyl isocyanate and a catalytic amount of 1,4-diazabicyclo- (2.2, 2) -octane are refluxed for three hours in 100 ml of toluene. After cooling, the solution is concentrated. After some time, a solid is obtained, which is filtered off with suction and dried. Yield: 39.3 g, mp 94 ⁰ C.

Example 125

15 4- (Phenylcarbamoyloxyethylthio) -2-methyl-5,6,7,8-tetrahydroquinoline

21.9 g (0.1 mol) of 4- (hydroxyethylthio) -2-methyl-5,6,7,8-tetrahydroquinoline are added in the presence of catalytic amounts of 1,4-diazabicyclo- (2,2,2) -octane 11.9 g (0.1 mol) of phenyl isocyanate are added in 100 ml of toluene at 100 ^{° C.} After stirring for two hours at reflux, the mixture is cooled and the solution is concentrated in vacuo to half its volume. Yield: 32.5 g, m.p. 145 to 146 "C

In analogy, the following were produced:

030047/0098

ORIGINAL INSPECTED

O U) O O

CD OO

E.g. Link .... yield
(%) Melting point
( ⁰ C) 126 4- (Cyclohexylcarbamoyloxyethylthio) -2-methyl-5,6,7,8-tetra-
hydroquinoline 76 150-1 127 4- (Ethylcarbamoyloxyethylthio) -2-methyl-5,6,7,8-tetrahydro-
quinoline 82 139-142 128 4- (Cyclohexylcarbamoyloxyethylamino) -2-methyl-5,6,7,8-tetra-
hydroquinoline 88 117-9 129 4- (Cyclohexylcarbamoyloxypropylamino) -2-methy1-5,6,7,8-
tetrahydroquinoline 80 107-8 130 4- (phenylcarbamoyloxyethylamino) -2-methyl-5,6,7,8-tetrahydro-
quinoline 94 143-4 131 4- (4 ^f -chlorophylcarbamoyloxyethylamino) -2-methyl-5,6,7,8-
tetrahydroquinoline 96 178 132 4- (i'-naphthylcarbarnoyloxypropylamino) -2-methyl-5,6,7,8-
tetrahydroquinoline 73 160-2 133 4- (4'-chlorophenylcarbamoyloxy-2'-propylamino) -2-methyl-
5,6,7,8-tetrahydroquinoline 80 148

JZ O

\O

CD

Cl

cn □

cn co

HOE 79 / F 809 (Ge. 604)

In the following examples 134 to 142, which are intended to show the biological effectiveness of the new substances, the letters A to W stand for the comparison agents mentioned below
5

A = flangan-ethylene-1,2-bis-dithiacarbamate B = N-C-trichloromethylthioJ-phthalimide C = Maneb-Zineb-Plischkomplex (Wancozeb) D = f1ethyl-1- (butylcarbamoyl) -2-benzimidazole-carbamate χ (benomyl)

E '= ^ Nergal S 40
F = ' ^R ' Mergal AT liquid
G = ^ 'flergal CAB 40
H = ^ 'Nergal AF

3 = 2- (1 ^Y lethoxy-carbanylamino) -benzimidazole

(R)

KS = ^v 'Mergal S 88 (zinc dithiocarbamate + substance = 3) L = pentachlorophenol

M = alkyldimethylbbenzylammonium chloride (Dimanin A)

Example 134

Tomato plant (Salanum lycopersicum) of the variety "Rheinlands Fame was achieved in the 3-leaf stage with those listed in Table 1 Connections treated soaking wet. The application concentrations were 500, 250, 125 and 60 mg of active ingredient / liter of spray mixture. A was used as a comparison agent in the same concentration of active substances.

After drying of the spray gas Bela, the plants were inoculated with a zoosporangia suspension of Phytophthora infestans and a day until dripping wet g9stellt of 100% in a climate chamber at a temperature of 15 ⁰ C and relative humidity. They were then placed in a refrigerated greenhouse with a temperature of 15 ^° C. and a relative humidity of 85 to 95 %.

0300A7 / 0098

HOE 79 / F 809 (Ga. 604)

After an incubation period of 7 days, the plants were examined for infestation with Phytophthora. The degree of infection was expressed in % of infected leaf area compared to untreated, infected control plants.

Table 1

l / erb, according to
example % Phytophthora infestation at mg active ingredient / liter
Spray mixture 250 125 60 100 500 0-3 5 5-10 33 0 0 0 5 60 0 0-3 5 5-10 62 0 0 0-3 5 59 0 0 0 3-5 74 0 0 0-3 5 73 0 0 0-3 5 34 0 0 0 0 80 0 0 0-3 5 132 0 3 5 15th Comparison
medium A 0 untreated, infi
adorned PfI.

25 Example 135

Grapevines obtained from cuttings of the Plasmopara-susceptible Cultivar Clüller-Thurgau were grown in the 4-leaf stage dripping wet with aqueous suspensions of the claimed compounds treated. The concentrations used were 500, 250, 125 and 60 mg active ingredient per liter of spray liquor.

After the spray coating has dried, the plants were inoculated with a Zoosporangiensusp9nsion of Plasmopara witicola to runoff and placed in a climatic chamber at a temperature of 20 ⁰ C and a relatu / s humidity of 100%. To

0300A7 / 0098

3?

βΚΤ-

HOE 79 / F 809 (Gs. 604)

The infected plants were removed from the climatic chamber for 24 hours and brought into a greenhouse with a temperature of 23 ^° C. and an air humidity of approx. 80 to 90 % .

After an incubation period of 7 days, the plants were moistened, placed in the climatic chamber overnight, and the disease was caused to break out. The infestation evaluation was then carried out. The degree of infection was expressed in % of infected leaf area in comparison to the untreated, infected control plants and is shown in Table 2.

Table 2

Verb according to
example % Plasmopara viticola infestation at mg active ingredient /
Liters of spray liquid 250 125 60 100 33
80
78
Comparison
middle:
B.
C. 500 0
0
0
3
10 0
3
3
5
25th 5
5
5
10
35 untreated, in-
fiz. plants 0
0
0
0
5

Example 36

Cucumber plants (variety Delikateß) were in the 2-leaf stage with 30 of a conidia suspension of cucumber powdery mildew (Erysiphe cichor-

acearum) heavily inoculated. After a drying time of the spore suspension for 30 minutes the plants were placed relative in a greenhouse at 22 ⁰ C and 90% humidity. DrBi days after infection, the plants were treated with the compounds and drug concentrations mentioned in Table 3

0300A7 / 0098

ZS

HOE 79 / F B09

604)

sprayed dripping wet. The scoring took place after 10 days. The degree of infestation was expressed in % of infested leaf area, based on untreated, infected control plants (= 100 % infestation).

Table 3

Verb according to
example % Cucumber powdery mildew infestation at mg li / irkstoff / liter
Spray mixture 250 125 60 30th 100 51
69.
Comparative
medium D 500 0
0
5 0-3
0
10 5
0-3
15th 5-10
5
25th untreated, in-
fiz.Pfl. 0
0
3

Example 137

Each time 0.02 ml of a bacterial suspension of Bacillus subtilis were placed in Petri dishes on nutrient media (standard I nutrient agar for Bacteria) applied drop-shaped; the agar were previously in liquid state the claimed compounds were added in the concentrations given in Table 4.

The plates inoculated with bacteria were evaluated after four days; the inhibition of growth was rated in comparison to the control (= inoculated agar without addition of active ingredient = 0 % inhibition).

Commercially available mercury-free products were used as comparison agents Products (E, F, G, H) that have the same active ingredients as the claimed ones Connections were applied.

030047/0098

COPY

39

HOE 79 / F 809 (Ge. 604)

Tabel

Verb according to
example inhibition in % of
material Bacillus subtilis
per liter of agar 50 mg active 61 1000 50 59 100 50 81 100 100 133 100 100 13.1 100 100 50 100 50 51 100 100 49 100 50 52 100 50 55 100 100 Comparison
middle 100 E. - F. 50 - G 50 - H 100 - 50 500 100 10 100 100 - 100 80 - 100 100 50 100 100 50 100 100 80 100 80 - 100 100 50 100 100 - 100 80 - 100 100 50 25th - - 25th - - 50 - - 25th - -

example

Methodologically, the experiment was carried out according to Example 137. Instead of Bacillus subtilis, the compounds were tested against Aerobacter aerogenes.

0300A7 / 009

ORIGINAL INSPECTED

HOE 79 / F 809 (Ge. 604)

Table 5

Verb. To
example % Inhibition of Aerobacter aerogenes at mg
Active ingredient / liter of agar 500 100 1000 50 0 60 100 50 0 59 100 50 0 65 100 80 0 86 100 100 50 50 100 80 0 49 100 Comparison
middle 50 0 3 50 50 0 H 50 50 0 K 50

Example 139

0.02 ml of a Biner spore suspension from Ulocladium consortiale was applied drop-shaped in Petri dishes to nutrient medium (Biomalz agar for fungi); The compounds claimed had previously been added to the agar in the liquid state in the concentrations given in Table 5. 6 days after the inoculation of the plates, the diameter of the fungal colonies on the agar was measured and the growth inhibition caused by the preparations expressed in %, based on the control (= inoculated agar without added active ingredient = 0 % inhibition). Commercially available mercury-free products (E, F, G, H), which were used with the same active ingredients as the claimed compounds, were used as comparison agents.

03004 7/0098

ΨΙ

HOE 79 / F 809 (Ge. 604)

Tabel

l / erb, according to
example inhibition in % of Ulocladium consortiale at mg
Active ingredient / liter of agar 100 50 10 5 1 0.5 51 1000 500 100 100 80 60 50 0 49 100 100 100 80 50 30th 0 0 69 100 100 100 80 50 30th 0 0 55 100 100 100 50 30th 0 0 0 1 / er. Equal-
nittel 100 100 E. 100 80 30th 0 0 0 F. 0 0 0 0 0 0 0 Q G 100 20th 60 0 0 0 0 0 H 100 100 80 0 0 0 0 Q 100 100

example

The tests were methodically according to Example 139 duroh-20 guided. The claimed compounds were here against Aureobasidium pullulans tested.

004770098

-JfS-

HOE 79 / F 809 (Gs. 604)

Tabel

l / erb.nach
example Hemnu ng in % of aureobasidium
mg of active substance / liter of agar 100 pullulans at 51 1000 100 50 10 49 100 100 80 30th 52 100 100 50 0 69 100 100 80 50 -55 100 100 50 30th 84 100 100 50 0 Comparison
middle 100 80 30th L. 50 100 - - 500 100 100 100 100 100 100 100

example

In each case 0.02 ml of a spore suspension of Xanthomonas citri were placed in Petri dishes on nutrient medium (organic malt agar for mushrooms) applied drop-shaped; the agar were previously in the liquid Condition of the stressed connections in the table 8 specified concentrations have been added. The plates inoculated with bacteria were evaluated after 4 days; this was the inhibition of growth compared to the control (= inoculated

Agar without added active ingredient = 0 % inhibition) rated. Tabel

Verb according to
example % Inhibition of Xanthomonas citri at mg
Active ingredient / liter of agar 125 60 30th 15th 48
33 250 100
100 100
100 50
80 40
50 100
100

Q300A7 / 0098

HOE 79 / F 809 CGa. 604)

Example 142

The unicellular green alga Chlorella vulgaris was treated in a nutrient solution (according to Döhler) in the logarithmic growth phase with the compounds listed in Table 9. The concentrations were 10 and 2.5 ppm active ingredient. The treatments were carried out in 100 ml Erlenmeyer flasks with 30 ml of algae suspension. The test vessels were placed on a shaker with constant bending (approx. 75 rpm) and continuous light (approx. 3000 lux). The values given in Table 9 indicate the kill rate in % compared to the untreated control. The evaluation was made 10 days after the treatment.

Table 9

Verb. 'After
example Algicidal effect against Chlorella vulgaris
Inhibition in % at ppm active ingredient 2.5 48
60
59
80
78
130
131
50
52
54
55
Comparison
medium Fi 10 95
100
97
100
95
90
90
100
97
85
100
30th 100
100
100
100
97
100
100
100
100
100
100
100

030047/0098

Claims (5)

branched alkyl radical with 1 to 12 carbon atoms, for a benzyl radical, for a phenyl radical, which by one or two chlorine atoms or by trifluoromethyl or by an alkyl radical may be substituted with 1 to 4 carbon atoms, for alkoxycarbonyl with 1 to 6 carbon atoms, for arylaminocarbonyl, where the aryl radical by halogen, -CF ₃ , -NO- or alkyl with 20 1 to 4 carbon atoms may be substituted can, for N-alkyl-arylaminocarbonyl, where the alkyl radical is one with 1 to 3 carbon atoms and the aryl group is substituted by halogen, CF ₃ or alkyl with 1 to 4 carbon atoms 25 may be substituted for aminocarbonyl for Alkylaminocarbonyl of 1 to 10 carbon atoms or is dialkylaminocarbonyl with 1 to 10 carbon atoms each, R is hydrogen, a straight-chain branch or branch th alkyl radical with 1 to 12 carbon atoms, a banzyl radical, a phenyl radical, which is replaced by one or two chlorine atoms, by trifluoromethyl or nitro or by alkyl with 1 to 4 carbon 0300A7 / 0098 HDE 79 / F 809 (Ge. 604) substance atoms can be substituted, an alkoxycarbonyl radical with 1 to 6 carbon atoms, a phenylthio, morpholino or piperidino radical, an arylamino radical, where aryl through 'Halogen or alkyl of 1 to 4 carbon atoms may be substituted, means or 1 2 R and R together represent -CH ₂ CH ₂ CH ₂ CH ₂ -, j R means hydrogen or an alkyl has a remainder with 1 to 4 carbon atoms, 4th
R is hydrogen, a straight-chain or branched one Is an alkyl radical having 1 to 12 carbon atoms, 15 R represents hydrogen or an alkyl radical with 1 to Carbon atoms, and R is hydrogen or an alkyl radical with 1 to 6 20 carbon atoms is while 7 R ⁸ A for a residue -SR, a residue -N ^ _, a Radical -S- (CH,) -0-CN ^, or a radical zn "γ 25 0 ) -0-C-NCw, with η = 2 or 3, LJ * ⁿ Il V
" 0 7 9
where R to R, Y and Y ^{1 have} the following meanings to have: R = a straight-chain or branched alkyl radical with 1 to 12 carbon atoms, an arylmethyl where the aryl radical
rest, Y by halogen or trifluoromethyl may be substituted, a 2-furylmethyl radical, a ß-hydroxyethyl radical, a ß- or «f'-hydroxy propyl radical or a radical of the formulas 030047/0098 --89-- HOE 79 / F 809 (Ge. 604) -CH ₂ COOH, -CH (CH ₃ ) COOH, -CH ₂ CH ₂ COOH, -CH ₂ CHCH ₂ OH, -CHCOOH, CH ₃ CO-, C ₂ H ₅ CO-, OH CH ₂ COOH CgH ₅ CO-, a phenyl radical substituted by hydroxy, 5- nitro or alkyl with 1 to 4 carbon atoms or can be substituted by -COOH, or a cc- bzui. ß-naphthyl radical or a cyclohexyl radical, R = a phenyl radical, which by one or ζωθί Halo- 10 - ■ genatome, trifluoromethyl, nitro, one or two Alkyl radicals with 1 to 4 carbon atoms, dimethylamino, -COOCH ₃ , -COOC ₂ H ₅ , 4'-chlorophenoxy, 2'-chlorophenoxy, 2 ^f , 4'-dichlorophenoxy, 4 ^f -phenoxy, flethoxy or ethoxy can be substituted, 15 a benzamido radical, a straight-chain or \ jev- added alkyl radical of the formulas -CH _ΛΛ or -CH ₀ CH,., Or _Xr 11 2 \ _R 13 20 -CH ₂ CH ₂ CH ₂ R ¹⁴ , where R ¹⁰ to R ^{14 have the} following meaning have: R =! Hydrogen, a 2-furyl radical, a ß-pyridino rest, a phenyl radical that is replaced by a chlorine atom or an alkyl radical having 1 to 3 carbon atoms or can be substituted by a 3,4-dioxomethylene radical, or a dialkylamino radical, mobei alkyl for 1 to 5 carbon atoms each or a piperidyl or 30 rorpholino radical or a bicyclo- (2,2,1) -heptyl- rest or a cyclohexyl radical, 11 R = hydrogen or methyl, 12th R sä hydrogen or alkyl with 1 to 3 carbons material atoms, 030047/0098 HOE 79 / F 809 (Ge. 604) 13th
R = phenyl, hydroxy, a dialkylamino radical with 1 to 5 carbon atoms in each of the alkyl chains, Methoxy or hydroxyethylamino, fl = dialkylamino with 1 to 5 carbon atoms in the alkyl chains, alkoxy with 1 to 4 carbon atoms, hydroxy, morpholino, N-methylpiperazino, Hydroxyethylamino or! "! Ethylamino, - R sä hydrogen or - but only in the case that R is phenyl - a straight chain or a disorganized one Alkyl radical with 1 to 5 carbon atoms or a hydroxyethyl radical, but also 8 9 R and R together for radicals of the formulas -N = CH-N = CH-, -CH ₂ CH ₂ OCH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -, ™ 3 can stand Y = alkyl with 1 to 18 carbon atoms, phenyl, the through C ₄ - to C_-alkyl, -Cl, -CF "or -N0_ can be substituted or benzo-fused, or cycloalkyl with 5 or 6 carbon atoms,
25th Y ¹ s = hydrogen or if Y stands for alkyl with 1 to 4 carbon atoms, likewise alkyl with 1 to 4 carbon atoms. 0300A7 / 0098 HOE 79 / F B09 (Ge. 604) 2. A process for the preparation of those defined in claim 1 Compounds of formula (I) (D, 7 R ⁸ in which A is a radical -SR or -W _g , characterized in that compounds of the formula (il) (II), in which R to R have the meaning given in claim 1, with the equimolar amount of a mercaptan of the general Formula (ill) or the equimolar to double-equimolar Amount of an amine of the general formula (IV) R ⁷ -SH (III) H-N ' (IW), 7 8 9 ωόwherein the meaning of R, R and R emerges from claim 1, in the presence or absence of an inert solvent at temperatures of 50 to 150 or 130 to 200 "C brings to reaction and from the hydrochlorides initially formed the bases by treatment with stronger ones Sets bases in freedom. 030047/0098 2818591 HOE 79 / F 809 (Ge. 604) 3. Process for the preparation of the compounds according to Claim 1, in which A = -S- (CH ₉ ) -0-CN ^ _v , or 0 -N- (CH ₀ ) -OC-nCwi with η = 2 or 3, U ^ ¹ ^ Il ' 5 "0 characterized in that compounds according to claim 7 7 with -SR, in which R stands for ß-hydroxyethyl, ß-hydroxypropyl or * -hydroxypropyl or those in which A = -N _q 9 8 R 10 - with R = H and R = ß-hydroxyethyl, ß-hydroxypropyl or ^ -hydroxypropyl, with the equimolar amount of one Isocyanate of the general formula (v) Y-N = C = O (V) in which Y stands for alkyl with 1 to 18 carbon atoms or for a phenyl radical which _{can be substituted or benzo-fused by C.- to C.-alkyl, -Cl, -CF "or NO 2} , or for cycloalkyl with 5 or 6 carbon atoms Atoms is in an inert solvent and in the presence of catalytic amounts of a base, or with the equivalent amount of a dialkylcarbamic acid chloride of the general formula (Vl) ^ NC-Cl (VI) ^Y 0 and is alkyl having 1 to 4 C atoms in the Y = Y ^1, in an inert solvent and in the presence of equimolar amounts of an auxiliary base in each case 20 to 150 ⁰ C. 030047/0098 HQE 79 / F 809 (Ge. 604) 4. Biocidal agents, characterized by a content of compounds according to claim 1 in addition to customary formulation auxiliaries. 5. Use of the compounds according to claim 1 as industrial fungicides and for combating leaf diseases and Seaweed. 030047/0098