DE1542710A1 - New fungicides - Google Patents

Description

The invention relates to new fungicidal agents which, as active ingredient, are a polyhaloethylthio compound the general formula

Ao? yy

^ H - 3 - C - CX ₅ j -

contain. In this formula aipd γ and at least "white" of the symbols X chlorine or bromine "j where the remaining IW symbols are hydrogen, QKLor or bromine, Ao is a phenyl-, para-phenyl-, or a lower alkane O (t« r m- {4Lederer) -alkylaaino-3ulfoiirest, E is a lower alkyl, allyl, ?henyl- or ijiraohlorphenylrest, or ea mean Ao and Ä auasusmen ait the N- atom om the Sucoinlaid-, Maleinimid-, aiutarirai * - "wter den Hyd * ntoin residue _f of 4a

BATH 0098U / 1976

5-position substituted by alkyl groups with 1 to 7 carbon atoms can be.

Biologically active compounds with the functional N-trichloromethylthio group have been known for a long time. Despite the long period of time during which the N-triotilor methylthio compounds are known, and the excellent effect which the N-iriehlormethylthiQderiwfc «as Fungicides and parasiticides have shown that no successful experiment has been carried out, homologues or analogues of these Bringing compounds into trade. The fact, that one laid feet on the N-triohlomethylthio group, shows the great sensitivity of biological effectiveness to structural changes »*. liiur i & el * es so it is very unlikely that the N- $ r ± chlorate ethylthio compounds can be improved

But it was found that the biological effectiveness with an H-PolyhalogenäthylvertinÄUCH fttff'tf «nigatena three halogen atoms, the emtwft & er fffc & ei * od ^ r bromine Bind, and few of them taue "ine" in cHJtleHwae iraa Sulfur atom is gebuodwi, weekly ^ trbfjeeitrt ^ n can.

.. _: j Dd.ee «Derivatives have a · bemeT *« yni ^ f ϊβ ^ · * ΐαϊβίΐ, which often go far beyond the "'"

Aiar lthjrl-

Imifenyl chlorides or bromides with the corresponding '' 'JMId orertmid or the metal salt of this compound !Getting produced.

Usually, the alkali metal salt in a gejlM-gnets inert medium suspended or dissolved, such as * In Beniol, toluene and wherein daa mixture was vigorously stirred in some cases in water, alcohol ttffcf t ■ Ü4S and>'ijgtwUlugfcht * is eye give ttulfenylhalogenid. The SuI-; _f ^J # "can nylhaleiffnid" la solution using a - 'inert solvent or without solvent ÄeAiums ice - _f iittel "uipegeben be. Suitable solvents are two! '; ^! Various hydrocarbons, such as petroleum ethers for Hezae ^ emieohe. After an appropriate heating process, the product can be filtered off or by removing the residue and isolating the solid product. The product can then, if desired, be converted. For representative connections

yeenresultae given in Table 1.

link Table It

Melting

analysis Yes

point , C Element Theory Found

ΙΤΤΤγΓ

% ; l- {ΧΛ * 2,2-tetraohlor- • ₍ ; #thyithio) -euooinimide 85-87

1,2,2-Iriohloräthyliyiiid

124-125

Eq Cl

47.5 40.6

47.1 40.0

H- (1.1,2-Srichloräthyl _ltil ttlio) -euooinimid 113-115 Gl 40.6 40.0

0098U / 1976

BATH

Table I (continued)

analysis fo

öchraelz-

",. , punict, ⁰ G Element Theory Found

Connection ^f

N- (1,2,2,2-tetra-

chloroethylthio) -

auccinimide 13l-132 Gl 47.5 47.3

N- (pentachloroethyl

thio) succinimide 123-125 Cl 53.6 51.5

N- (1,1,2,2-tetrachloroethylthio) -

diglycolimide 81-85 Gl 4 5.4 4 5.4

N- (1,1,2,2-tetrachloroethylthio) - glutarimide

N- (1,1,2,2-tetra-

chloroethylthio) maleimide

N- (1,1,2,2-tetrachloroethylthio) -2,3-dibromosuccinimide

78-81 N
S. 4.51
10.3 4.73
9.7 65-68 a
N 10.9
4.8 11.3
4.9 107-108 S.
01 7.07
31.2 6.66
32.4

isHe for products from the Hyüantoin group sinci given in table II:

0098U / 1976

_ 5 -
Table II:

Analysis ° / o

Melting connection point, ⁰ G element calc.

chlorethylthio) -5,5-dimethylhydantoin 190

3- (1,2,2,2-tetra-

ehlorä thylthiο) -5,5-

aimethvlhydantoin 151-164 Gl 43.5 43.4

3- (1,1,2-trichloroethyl thio) hydantoin 145-148 Gl 40.4 39.0

S 12.1 11.7

chioräthylthiο) -

5,5-dimethyl -

hydantoin 196-199 Cl 43.5 43.0

3- (2-chloro-1,2,2-t ri b romä thylthi ο) -5,5-dimethyl -

hydantoin 187-189 Cl
Br 7,
52 7th
, 2 8th,
52 1
,1 3- (l, l, 2,2-tetra-
cnloräthylthio) -
hydantoin 158-160 Eq
S. 47
10 , 7
,8th 47
11 ,8th
, 6 3- (2-bromo-l, l, 2-
trichl orethyl thio
hydantoin 157-158 Cl 31 ,1 33 , 2

3- (pentachloroethylthio) -5,5-dimethylhydantoin 183-187 Cl 49.2 49.3

3- (1,1,2,2-tetrachloroethylthio) -5- (l-ethyl-

hydantoin 112-114 Cl 35.9 32.7

S 8.1 7.5

lied, inag,

0098U / 1976 ^8AD

- 6 Table II (continued)

_c . _Ί analysis

melting *

Connection point, ⁰ G element ber.

3- (l, l, 2,2-tetrachloroethylthio) -5,5- (2 ', 2, 4'-ϊγ1-methylpentamethylene) -

hydantoin 2Ü6-2O9 01 34.7 31.7

S 7.8 7.7

Methy 1.-2,4-dioxo-N-

(1,1 ', 2,2-tetrachloro-

ethylthio) -thiazo-

Iidyl-f5j acetate oil Cl 36.6 36.3

'Ee was not an individual analysis for each halogen obtain. Only the total number of milliequivalents of halogen that was present was established.

; Table III gives the analytical results for sulfonamides.

Table III;
P analysis ($)

! Melting point

' ; ⁰ Q element calc.

Ιί-4-Ohlorphenyl-N-
'. (1,1,2,2-tetrachloräthylthiο) -ethanaulfonamid 126-128 S "15.3 15.3 ι

N-methyl-N- (1,2,2- ■ trichlorovinylthio) -4-chlorobenzenesulfonamide 98-100 Cl 38.6 38.2

0098U / 1976

- 7 Table III (continued.

87-88 analysis 29.5
7.7 (tf) 72-75 Element over. 37.0 found Melting point
Connection o _n 103-105 (Jl
N 44,] 31.0
8.0 H-phenyl-N- (1,2,2-tii-
ohlorvinylthio) -di -
methylaminosulfon-
amide Cl 37.0 H-ithyl-N- (1,2,2,2-
tetrachloroethylthio) -
benzene sulfonamide Eq 42.3 N-methyl-N- (1,2,2,2-
tetraohloräthylthio) -4-
ahlor-beneolsulfonamide

120-122 Cl 44.1 42.7 118-12? Eq
Br 31.7
17.8 31.9
17.5 119-121 Eq
Br 27.1
32.4 25.0
30.1 71-75 01
S. 47.5
14.3 47.8
14.8

I-Phenvl-N- (3,2,2,2-

tetraohloräthylthio) - dimethylaminosulfone

aaid 92-96 Gl 35.6 35.0

I-methyl-N- (1,1,2,2-tetrachloroethylthiο) -4-chloro-benzenesulfon-

H- (2-bromo-l, 1,2-tT-dichloroethylthio) -K-methyl-4-chlorobenzene sulfamide

H- (1,2-Dibrora-1 _t 2-dichlO2 «thylthio) -N-methyl-4-chlorobenzenesulfonamide

I-Jiethyl-H-pentachloril thyl thio-4-chi ο rb enzoleulfonamid

0098U / 1976 bad original

Table III (continued)

j
I. Melting point j connection ° C V / * zJ SO ₀ N \ j-zt Analysis (#) ber. found T Cl 26.4 «Ef. • Ζ ΛΛ , N-AlIyI-N- (1,1,2,2-, J ⁴ 7 T * 1 O 26.4 ί »2ϋ j tetrachloroethylthio) - element ± 1.9 16.80 benzeneBUlfonamide 60-61 ί SO ₂ C ₄ H ₉ 16.2 16.3 a ¹ 10.9 39.12 Connection R Ac Analysis (#) Cl 7.54 S. Element over. DEAD 36.2 17.70 N-dodecylphenvl-CcHc SOpGH, SO ₂ IT ^ ² Cl JM 37.58 N- (l, l, 2,2-tetra- ° ^p C. S. '»± t> ! chloroethylthio) - O Cl O, Ip methane sulfonamide ' ^H 5' M 16.35 17.16 S. 36.38 36.80 N-methyl-N- (1,1,2 _T CH, 2-tetrachloroethyl 3f 58 thio) dipropylamino- 16.58 sulfonamide 39.10 N-Butyl-N- (1,1,2,2- C.H, 7.68 tetrachloroethyl- ⁴ - 17.60 thio) butanesulfone amide N-methyl-N- (1,1, CH,
2,2-tetrachloroethyl- ° thio) diethylamino sulfonamide

The compounds of the present invention are major useful for their biological effectiveness. The following tables not only show the superiority of the new ones

0098U / 1976

Compounds according to the invention compared to the previously known analogous compounds, but also the sensitivity to biological activity Structural changes.

Any compound that has been tested for fungi toxicity was dissolved in acetone at the degree of dilution expressed in parts per million in the table. Paper sheets, which had previously been inoculated by impregnation with equal amounts of a fungus culture broth were "

added to potato-extractrose agar medium and ee was an exactly equal amount of each fungicidal solution brought to their midst. After treatment with the respective compound, the leaves were treated with inoculated, however, untreated control leaves are incubated at ambient temperature until untreated Leaves were filled with mycelial growth. The leaves were put on an agar medium and the fungitoxic Effectiveness of the chemical compound was based on a comparative determination of the radius of the Myeelwashiturns the agar medium, omitted from the hand of the leaf, - at "be I

traded and untreated samples found »Bas! |

The ratio of these radii results in a percentage In- i

fection. After deduction of 100 i "by the biological efficacy of the tested toxic agent is expressed the Funguswachstums receives oaan dia percent inhibition. . · ':

In Table IV are various derivatives with the li-ljl ^ tZ-Tetrachlorilthylthiogruppe resembled a modern srfiiidungs new functional group _{with derivatives of the known functional N-chi Trl omethyltMogruppe τ γ · # "

009814/1976

ITi

₁ 1.2

125

yrichloannethyl

125/125 / ^'12 5 /

/ _{125/125/7 27} '15 '24

'1OO' 100 '100

125/500 /

100 Ί00 / 100 '78

^{1000/1000/1000} Z., / Q6 / 99 '63

250 /

1000/1000/1000 /

/ AO '21 '70

I T. Terticilium

• ft ··· tr κ · ■

- 11 -

i iff "

■ i

-ν

it

Results clearly show the significant i fungicidal activity of the compounds against erfindungege {Baden to the previously known analogous compounds, as well as the strong reduction of Wirkeamkeit of Polyhalogenäthylthioverbindungen when the ^ thylgruppe is outside the range of the present invention.

Table V shows the fungicidal effectiveness of various acyl derivatives with various Poiyhalo _f :; enäthylerugrpen falling within the scope of the present invention . *

Table V: link

Organism ⁴ "^;

L, 2, fT et raohl or-, ^ ^ i thio | -§- <l-ethyl- -lifpmyl ) -hy <l4ntoin

»-1 ₁ 1,2,2-Tetra.ohlor-. Mthylthio-fi-methyl benzene * ^r 'Bulfonamid

- R

• fcjhto-H-phenylbenzene aulfon-Mid

«3-Pentaobloroethylthio-55dltilhdti

3 »{2-BrOm-l, l, 2-trichloro ethylthio) -5,5-dimethylhydantoin

- H

Concentration, parts / hilllon. Percent inhibition

1000

100

100Oy

100

1000

99

1000

100

250

95 98

500

100

009814/1976

BATH

W -

TS42T10

■■ 'It,

- 12 -

t ■ '■:

Table Y (cont.)

link

organism

5- (l, l, 2,2-tetrachloroethyl
ünio) hydantoin

y (,,,
ehloräthylthio) dipropylamino-sulfonamide

HPR concentration, leile / million, ρroeent. inhibition

250 /
1000

100

100

1000

100

500

* ■ ν t

H-Bfttyl-lJ- (l _f 1.2 _t 2-tetra-

ehloräthylthio) butane eulfonaniid

H-methyl-M- (l, l »2,2-tetra

ehloräthylthio) diethyl

iMttinoBulfonamid

_u ^H

HP ^5ΟΟ / δ1 ^500/97

500

500/100

H β Helminthosporium; P «Fueariuaa; R = Rhizoctonia.

Various compounds according to the invention, a compound produced by the previous process with a 4-functional H-triohlorraethylthio group and one of its derivatives, which by incorporating a methylene group Kwisehen the sulfur atom ua4 the tri-

009814/197 6

. ..ohlormethylgruppe was obtained, were tested for their fun- 'gizide effectiveness after under the title "The Standard Spore slide Cfrermination-Method for Determining
Fungicidal Activity "in the American Phytopathological Society Journal, Vol. 33, pp. 627-632, Volume 1943. This method is used to measure the fungitoxic activity of funglaid ohemiaic compounds. The activity is expressed as |

percentage inhibition of the germ of fungus spores expresses.

Every compound that was examined was made
dissolved in acetone at a dilution ratio of 10 parts / million and 3 l / million. These solutions were then i plpettiert in-well microscope slide and \ dried. The wells were filled with a spore suspension of the test organism, Monilinia fructicola ,, ^l

filled and incubated overnight in a humid chamber. A group of 100 spores was examined and the number of germinated and non-germinated spores was determined! ■ ■ - _; de counted and applied to the biological-effectiveness to show '.' ■ 'I ness as percent Keimheaiaung.

The results of these Veroueke are in TaT »» U · reproduced.

BATH ORIGINAL

.001114 / 1971-

1*

»BJT - · ■ ' rs- ·· -.' · '■■ ■■■ ·

-3. _t 2

-I- & thyl-

»-1,1,2, a-

I-l, l, 2,2-feiiraelilor * thylthio-irlilfid

1-1,1,2,2-f * tr »ehlor» thylthio-I- »• tiyl-p-» lbllfiia

! • 1,1,2, 2-

1-1,2,1,2-tetracliloroethylthio-S-il1lXfoamiid

dim thy lhydant oin

I- (1,2-B4> xom-l _f 2-diohloroethylthio). ! - «• thyl-p-chlorobenzene oleulphonamide

11 "TI"

X. Pruotiool *

tonaantr

antr. 10 tells / mill. } ϊ ^, ΐβ / ilill.

98

100 100 100 100 100 100 100 100 100 100 100 100 'WHERE 100

100

"O

N-1.1

H-1,1 _t 2 _f S-bemsolaulfonaaid

t ttr Up xaA R iueuiia)

M. Pructicola Prosmtual · Ht

itr- 10

42

100

It turned out that the group of the invention ate Connections to the best analogous connections produced by the previous processes Control of many diseases caused by a fungus is equivalent or, in most cases, far is superior. It was completely unexpected that when compared with the previously known analog compounds and inr .Derivate the group of the invention Connections would have this clear superiority.

Except in the compositions and use forms described in the preceding examples the compounds according to the invention can be in or on inert liquid and solid carriers, e.g. inert clay, xylenes, etc. may be dispersed. The solid support can be used as dust or in conjunction with a suitable wetting agents can be used to produce a wettable powder. The fungitoxic according to the invention Compounds can also be made with other solvents, dispersants or emulsifying agents be mixed. Furthermore, these compounds can not only be used on their own or in a mixture with other compounds of the group according to the invention can be used, but they can also be mixed with other active toxic Substances used in the compilation of agriculturally valuable means for controlling plants Infecting epidemics or diseases are used.

The compounds can also be applied to a surrounding area that hosts or hosts the fungus

009814/1976

“ ^BATH

where there is a risk of fungus infestation. For example the fungicidal compositions can act directly on a plant or other host, sprayed or otherwise applied to the plant seed, soil or other plant environment or similarly used to combat fun gus and the diseases it causes.

The following Tables VIII-X contain the results of further comparative tests.

bath 009814/1976

15 * 27tO

- 18 -. Table VIIIt

Myoel-inhibiting effect of sttocinimi according to the invention (fd «lvate versus helmet! Nt ho ep ο rl um in comparison« it ^ -ThI οι ri chi ormethylsucclnimid (geffläfl PBg 887 506 ).

Serial - link 0 Cl
I. - Cl I. 0 Cl Cl -H Inhibition fin ^ t) - No. H
- C - C ■ H t I. HelminthOBWprium , I. IH ₂ C - - C - C ■ - C 500 parts / lgl. - ■ C ^ Cl i
j \ I. I. Ho-C I. (Comparison) | h ₂ c - - Ο * S. Cl ί C.
I. 0 f H i
> 59 HoC 0 Qf. Ho-C 0 01
I. Cl \ C. M.
C. C - C- H ₉ C Cl m C. 2 0 100

§99814 / 1976

- 19 - Table IXi

erfindungagemäßer Polyh alogen-

zocionla in comparison

opposite lo rbenEplaalfonaa id, T75J.

Compound escapement Rhlzoctonia 1000 pieces / million

- H-S-C-Oil

O 01 ( Y9TgI eiohaeub punch)

BATH

0098U / 1976

■ ■ ** »■ * r

Table IX (cont.

Serial
No. C ₂ H ₅ - link CH,
I J y Cl Cl
I. Cl Inhibition (%)
Rhizoctonia
1000 pieces /
million I.
I.
i 94 I. 100 VJI ° Jl -H-B- "^ Cl
I. - CH
I.
Cl / - \ Il / ^ S τ- C
I.
Cl Cl Cl
II 100 "a
O C ₆ H ₅ C-C- 6th O CH,
Il I ■> - N - S - S - I I 99 ^ S-N- Cl Cl O
/ —Ν " Il Cl
I. \ / ^S O -Cl
I. CH O C - Cl ■ 7 O
r— \ Il Cl Cl
I. \ y ^S Cl
I. CH θ '* Il C - I. O I. Cl Cl

0098U / 1976

bath

Table X:

Mycelhemmende effect erfindungagemäßer Hydantolnderlva- "fce over a wide en en Orga ni smen compared to N;

Thiotrichloromethyl-5 _t $ -dimethylhydantoin (according to U.3. Pa-

- ^ 775).

Serial

No.

Compound inhibition (in H.

Rhizoctonia

Parts /
Mill.

Fusarium

1000 parts / mill.

Ii-S-G-Eq

NH-G

Cl

(Comparison substance) 35

40

NH-C

D Cl

NSC-CH ₉ Cl / ι <-

Cl

80

Cl Cl

^! 3 ! 4th CH ₀ j ^ N-S-C - j I. Cl C.
I. 'C ₄ Hq - C-H Cl • ~ ⁰ ^ Eq I. C-H NH O Eq ■ \ // Cl 2 5 CH-CH-C ^ Cl ¹ / y ^N HSC - ^χ I / NH-C ^s o

100

100

BATH ORIGINAL

009814/1976

Claims (1)

Claim; Fungicidal agent, characterized in that it is a Polyhalogenäthylthioverbindungennng as an active ingredient the general formula contains, in which Y and at least two of the symbols X are chlorine or bromine, with the remaining X symbols Are hydrogen, chlorine or bromine atoms, Ao is a phenyl, parachlorophenyl or lower alkane or di- (lower) -alkylamino- * ulfone radical, R is a lower level Alkyl, allyl, phenyl or parachlorophenyl radical, or Ac and R together with the N atom denote the suocinimide, Maleimide, glutarimide or hydantoin radical which can be substituted in 5-3 position by alkyl groups having 1 to 7 carbon atoms. For California Research Corporation tDr. H.J. Wolff) lawyer Ä098U / 1976 ,. ^ ^BAD original ^ BlSl UnttrilQWV (Art711 ** aNr.ISMt3 «μAadvww ·. * 4.9. U * ..