DE1953431A1 - Saturated aliphatic alpha [N- (3,5-dihalogenophenyl) -carbamoyloxy] -carboxylic acids, their alkyl esters and corresponding thio compounds, processes for their preparation and their use as microbicides or in antimicrobial agents - Google Patents

Description

DR. ELISABETH JUNG, DR. VOLKER VOSSIUS, DIPL.-ING. GERHARD COLDEWEY

Patent attorneys
8 MÖNCHEN 23 CLEMENSSTRASSE 30. TELEPHONE 345067 · TELEGRAM ADDRESS: INVENT / MONCHEN. TELEX 5-29688

Oct 23, 1969

uZ * B 730 (Pi / J / kä)
DP - 5261 p

SUMITOMO CHEMICAL COMPANY, LTD ₀ ,
Osaka » Japan

"Saturated aliphatic M ~ / N- (3? 5 ~ Mhalogenphenyl) ~ carbaaoyloxjr / '- carboxylic acids, their alkyl esters and corresponding thi ο compounds, processes for their preparation and their use as microbials or in antimicrobial agents ^H.

Priority: November 27, 1968, Japan, No. 87 108/68

The object of the invention is _for novel compounds which can be used as microbicides or in antimikrabiellsn means "and to provide a process for the production thereof.

The invention relates to compounds of the general formula I

R.
-NH-CZ-CH-COCR

(D

In which the radicals X mean halogen atoms, the radicals Y and Z are identical or different and oxygen otter means sulfur atoms

BATH

and the best R and R ^{1 are} identical or different »ind and hydrogen torae or lower alkyl radicals mean ·

The halogen atoms X can be chlorine, bromine or iodine atoms · The term "lower" refers to Allcylreate R and R * alt 1 to 5 carbon atoms, viio methyl, ethyl ,; Propyl, isopropyl or butyl groups o

The general formula I thus relates to the following four Types of connections:

a) Y = oxygen atom, Z »oxygen atom» saturated aliphatic (3,5-dihalo ^ enphenyleerbamoyloxy) carboxylic acids and their lower allyl esters;

b) Y »sulfur atom, Z» Saueratoffatο »:

saturated aliphatic tf- ^ ~ (3,5-dihalophenyl) - * tnlooarh * - moyl / carbonic acids and their lower allyl esters;

c) Y = oxygen atom, Z - sulfur atom

saturated aliphatic ^ ί-Ζκ-ί 3 ₁ 5-dihalophenyl) -oarbamoyl · »thiq7-carboxylic acids and their lower alkyl esters;

d) Y · »sulfur atom Z = < Sulfur atom:

saturated aliphatic δf- / N- (3,5 «dihalophenyl) -thiocarbamoylthiq7-carboxylic acids and their lower allyl esters ₀

Examples of the compounds of general formula I mentioned above under (a) to (d) are lower saturated alipha ™, tables of - »/ ίί ~ - {3,5 ~ Dihalogenphenyl J-carbamoyloxyy-earbonBauren and their lower alkyl esters _? such as N- (3,5-dichlorophenyl) -carbamo ~ yloxyessig ", N- (3,5-dibromophenyl) -cart« aioyloxyesaig », of- / JN- (3,5 ~ dichlorophenyl) -carbamoyloxx7-propion * - or

00 ** 25/2124

* - (3 »5-Diohlorphenyl ^ -oarbamoyloxycesigeUuremethyles ter, I- (3 »5-3> chlorophenyX) * - carl) amoyloxye88lgsäureäthy! Ester or d- / if- (5 · 5-Diohlophenyl) -carbamoyloxypr opionsäureäthylee ter, lower saturated aliphatic <* - / [& - (3,5-Dihalofc enpheny I) - thioosxbaiioylox ^ -oarboxylic acids and their lower allyl esters, such as

-acetic-, H- (3ι5-dichlorophenyl) -thiocarbamoyloxy- N- (3ι5-dibromophenyl) thlooarbejioyloxyeeaig- or α- / H- (3 _r 5-Diohlorphenyl) -thiocarba- oyloxx7 ■ * P ^ro pi ° ^{nB acid} or M- (3 _p 5-dichlorophenyl) ~ thiocarbamoyloxyesBigtäuremetnyleeter, U- _{3-f 5 Diohlorphenyl) -thiooarbamoyloxyeseigaäureäthyleeter or σ; - ^ N- (3,5-dichlorophenyl) -thiocarbauoyloxy ^ -propionic acid ethyl esterp lower saturated aliphatic Of ~ / il- (3 # 5 "-Dinalogenphenyl)" CQrbamoylthio7carboxylic acids and their lower alkyl esters, such as N- (3,5 -Dichlorphenyl) -carbaeoylthioeesig-p I- (3 »5-Dit» rflmphenyl) -oarbamoylthioeeoigr or Λ- / Ν- (3,5-dichlorophenyl) ~ oarbamoylthio7-propionic acid or K- (3,5-dichlorophenyl) - 'oartaBoethylthioesäureaige _r N - (3 ₉ 5-dichlorophenyl) - oarbamoylthioessigeäureäthylester or öf- ^ il- (3 ₁ 5-Dl chi or phenyl) ~

and oarbamoylthio / ^ propionic acid ethers / lower saturated alipha tieohe OE / H - (3 "5-Dihalogenpheny 1) -thiooarbaaoyltliio7 ~ carboneäuren and their lower allyl esters such as _t M- (3,5 ~ dichlorophenyl) -thlooarDfuacylthloeaeig-, H- (3 _f 5-dibromophenyl) -thiocarbamoylthioesiig- or V - £ k- (3 j 5-dichlorophenyl) - thir.oarbaaoylthio / propionic acid or M- (3r5-Diohlorpheiiyl) 'thiocarbanoylthioeigeäure- »ethyleter _r H- (5 * .5-dichlorophenyl) -thiocarba« oylthioeB8ig8 or q - /> - (3, 5-dichlorophenyl) -thiocaxoamoylthiq / -propione acid ethyl ether.

The invention also relates to a method for producing the Compounds of the general formula I _? that is characterized by

ÖÖ9825 / 2124 ^ M2 €)

BATH

net is that a 3,5-dinalogenphenylieooyanat or -ieothio-

cyanate of the general formula II

/ \ (II)

in which the radicals X and Y have the above meaning, with a

Compound of the general formula III HZ-CH-OOOR '* (III)

in which the radicals Z ₁ R and R ^{c have} the above meaning, brings to implementation.

Specific examples of 3 »5-Dihalogenphenylieooyanate and -isothiocyanate of the general formula II are 3 _# 5-Bionloropnenylisooyanat, 3,5-Dibroophenylieocyanat, 3,5-Dichlorphenylieothiocyanat and 3f5-Dibroaphenylisotniooyanat formula III) aindt GIyKoX- and Xhioglykoleäure and hctnylglykolat, Athylglykolet _P HetbylthioglyJcolat "Athylthioßlykolat, Hethyllactat, Äthyllactat, Hethylthiolaotat and Xtbylthiolactat.

You can use the 3,5-DihalogenphenyliBocyanat or «thiooyanat with the compound of the general formula III, optionally in the presence of an organic Baee, such as pyridine, triethylamine or H-methylmorpholine, at temperatures from room temperature to ssu Reflux temperature in an inert solvent such as benzene, React toluene, xylene, diethyl ether or chloroform. The reaction usually takes several hours. Dungegemäsee compound of the general formula I by adding the

009825/2124

IBAD ORIGINAL

The solvent evaporates from the reaction mixture.

The invention finally relates to the putrefaction of the compounds of the general formula Z as Mlkrobiside or In anti-crobial agents.

It has been found that the compounds of the invention the general Poimil I have a strong antimicrobial effect on the most varied of microorganisms, such as pbytopathogenic pils and parasites occurring in industrial products. This is surprising, since homologous compounds such as the corresponding compounds not halogenated in the 3,5-position, no special effect in this respect on catfish

Specific examples of phytopathogenic fungi versus which the compounds according to the invention have a strong antimicrobial effect, are Pirioularia oryssae, Coohliobolus miyabeanuB, lanthoaonas oryzae, Sphaerotheca fuliginea, Pellicularia saeakii, Pellioularia filamentosa, Pusarium oxysporum, Corticium rolfsli, Botrytis cinerea, Sclerotlnia eclerotiorum, Alternaria kikuohiana, Alternaria mali, Glomerella olngulata, Pythium aphanidermatum. Am An example of the industrial product parasites that can also be controlled is Aspergillus longer.

(X -ίί- (3,5-Bichlorphenyl) -thlocarbamoylthioeseig8äureäthylester has z, B _{0 on the} following fungicidal and antibacterial spectrum obtained by the agar dilution method

009825/212 *

Table I.

Teötorganiamus Minimal Hewakons-
tration. H > Piricularia oryzae 0.0008 Xanthomonas oryzae 0.004 PelIicularia 0.004 Fuaariun oxysporum f. Niveum 0.004 Corticium rolfsii 0.0008 Botrytia cinerea 0.02 Sclerotinia sclerotiorum 0.004 Alternaria kikuohiana 0.004 Alternaria mali 0.004 Glomerella cingulata 0.0C08 Aepergillus niger 0.004

The compounds of the general formula I according to the invention can be used as agricultural chemicals to prevent or inhibit plant diseases caused by phytopathogenic fungi be used. It can also be used as an industry »· Use chemicals that prevent or inhibit pest infestation from industrial products prevent staining ο

Han can use the compounds of the general formula I according to the invention. In practice, however, they are diluted with a suitable carrier material and thus conventional preparations are made, such as dusts, wettable powders, oil sprays, aerosols, tablets, emulsifiable concentrates , Pellets or granules ₀ These agents can also contain one or more known fungicides, such as blasticidin S ₇ kasugamycin, polyoxin, cellocidin, chloramphenicol, 0,0-diethyl S-benzylthiophosphoric acid ester, CA "thy 1-S, S-diphenyldithiophosphoric acid ester, On -Butyl-S-ethyl-S-benzyldithiophosphoric acid ester _ft O _s O ™ Diisopropyl «-S *> benaylthiophosphoric acid ester,

009825/2124

BATH

1953A31

O-Xthyl-S-beneylphenylthiophosphoric acid ester, pentachlorobene "- aldoxi", pentachlorobenzyl alcohol, pentachloromandelic acid nitrile, pentaohlophenylaoetate, Kieenaethylareonat, KieenamaoniUBiaethylaraonat, ^ "- , 2-bii- (p-chlorophenyl) -ethane _f 0,0-dimethyl-O ~ (p-nitrophenyl) -thio ~ phosphoric acid ester, 8- / 1,2-bia- (ethoxyoaibonyl ) -4kttoylJ ~ 0 , 0- dl ~ »tthyldltlilophoephorBäureeeter, O, O-Dlmethyl-S- (I-eethjloarba-» oyl) -dithiophoephorsÄureeater _t O-ethyl-0-p-nitrophenylphenylthlophoiphoneaureester, a-Kaphthyl-Dinethyl-Hiatylo-0,0 0- (i> -nitro-ai-diethylphenyl) -thiophoephor8 acid ester, 3 · 4 »516-t · trahydrophthalinidoethylchrysanthemate, 3 # 4-urethy1-ph« nyl-1hiethyloarbÄ »at, O, O-diethyl" O- (2 ~ ieopropyl-6- »ethyl-4-pyrimldinyl) -thiophotphat, O ₉ O-Dlnethyl-2,2-diohiorrinylphosphat, 1, l-bending (p ~ chlorophenyl) -2,2,2-triohloräthanol, 1, 2- Dibroethane, 1 _f 2-dibro «-3 ~ chloropropane, zinc-ethylene-bis-dithiooarbamate, manganese-ethyltn-bis-dithiooarbamate, 2 , J-dichloro-l ^ -naphthoohinon,

Tttraohloräthylthio) -4-cyolohexen-1,2-dlcarboxleid, cyolisches 6-4 (ethy1-2,3-quinoxalindithlolcarbonat, Tetraohlorieophth & leäurénitril, Matriuii-p -dimethylaminobensoldiasoeulftaat ^, 4-Dihlor-6- (2-8-chloroanilino) -triazine, 2,4-dich] .orphenoxyeeeigeäure, 4'OUpr ~ 2- * ethylphenoxyeB8ig8äure, 3 % 4-Diohlorpropionanilid _c 2,4-Diohlorpheny1 ^ 4 * -oitrophenylather, 2-Chloro-4,6-bis- (äthylaaino ) ~ a ~ trlaEin and Hatriua-N- (l-naphthyl) -phthalamato These antialcrobial agents can also contain one or more compounds with ineecticidal, neaatocidal, acarissidal or herbicidal action, as well as fertilizers, soil treatment agents, soil infectants or plant overgrowth regulators for typical antimicrobial agents

009825/2124

(a) Dusts obtained by dispersing at least one compound of the general formula I as an active ingredient in a concentration of 0> 1 to .50% by weight in an inert carrier material! such as talc, diatomaceous earth, wood flour or clay,

. th will;

(b) wettable powder obtained by dispersing at least one Compound of the general formula Z as an active ingredient in a concentration of 0.1 to 80 wt. an alkali salt of an alkyl sulfate or a partially neutralized sulfuric acid derivative of a mineral oil, a naturally occurring glyceride or a condensate product of an alkylene oxide with an organic acid * will;

(o) Emulsifiable concentrates, which are obtained by dispersing at least one compound of the general formula I as an active ingredient in a concentration of C ₉ I to 30 wt getting produced;

(d) Granules, dusts and aerosols that make up the compounds of general formula 1 and in the usual way getting produced.

The examples explain the origins of parts and percentages refer to the weights

009825/2124

BATH

«. Q _w

Establishing a compound of the general formula It

A mixture of 0.1% of a 3.5% halogenophenyl isothiocyanate or isothiocyanate of the general formula II, a little pyridine as a catalyst and 50 ml of propyl ether is added dropwise to a 200 ml flask with stirring with a solution of 0.1% Compound of the general formula XII (a glycolic or thioglycolic acid or a corresponding ester) is added to 5C ml of isopropyl ether. The mixture obtained is refluxed for 1 hour. After cooling, the precipitated crystals are filtered off and dried. A compound of the general formula I, ie a lower saturated aliphatic (3 »5-J) ihalophenyl) ~ earbamoyloxx7-carboxylic acid, a lower alkyl ester of such an acid or a corresponding thio compound is obtained in excellent yield _β

Table II lists examples of those made by the above method compounds of the general formula according to the invention

009825/2124

Table II

Out of all connections rlycol or
Thioglycolic acid
re or their
Ester (111) product Connection of
general
Formula (I) Pp., ⁰ C AU8-
beu- Analysis.
calculated, f »
(found, 5 ») C. H Ji Cl S. O 3,5-dihalogen
phenyl isocyanate
oaer -isothio-
cyanate (II) Ethyl lactate chlorophenyl) -
carbamoyloxy / ~
propionic acid
ethyl ester ■ 75.0-76.0 95 47.08
(47.24)
,; 4.28
(4.01) 4.58
(4.48) 23.16
(22.97) 3 _S 5-Diohlor-
phenyliso-
cyanate Ethylthio
glycolate chlorophenyl) -
carbarnoylthio-
esaetic acid
ethyl ester 136.0 -
137.0 93 42.87
(42 _f 46) 3.60
(3.50) 4.55
(4.53) 23.01
(22.80) 10.45
(10.18) 3 s5 ~ dichloro ~
phenyliso-
cyanate Ethylthio
glycolate chlorophenyl) -
thiocarbamoyl
thioessxgeic acid
ether 115.5 -
117.0 90 40.75
(40.63) 3.42
(3.26) 4.32
(4.49) 21.85
(21.77) 19.78
(19.41] 009825/212 3,5-dichloro "
phenyl! so-
thiocyanate Ethyl"-
1-actat thiooarbamoyl
acid ethers 50.0-54.0 84 44.73
(45.12) 4.07
(4.22) 4.35
(4.15) (21.63.) 9.95
(9.20 3,5-dichloro
thiocyanate Glycolic
acid H- (3,5-dichloro-
phenyl) -carbamo-
yloxyesaiga acid 156.5 -
158.5 91 40.93
(40.84) 2.6?
(2.77) SI, 30
(5.31) 26.85
(26.53) · » 3,5-dichloro
phenyliso-
oyanate Thioglycol
acid H- (3 »5-Diohlor-
phenyl) ~ carbamo-
ylthioacetic acid 122.0 -
124.5 90 38.59
(38.92) 2.52
(2.69) 5.00
(4.98) 25.31
(25.56) 11.45
(11.33; phenyliso-
cyanate

Example 2 Production of a dust agent

3 feil · <* - / fc- (5,5-Diohlophenyl) -carbamoyloxyj7-propionsttureäthylester and 97 ropes Tan are reduced in size and mixed well « IUn provides a storage medium which contains 3 Jt of active substance and all as long as ·· can be used »

Example 3 Production of a · dust & ittelss

4 ropes * - /! - (3,5-Diohlorphenyl) -oarb € uioylthio7-eeBieeäureäthylestr and 96 file falcon are "" explained and well approved. Nen is a stubber agent that contains 4 Jt of active ingredient and is used as a solohes can be used

Example 4 Making a beaetsbaren:; ■ '' jt ^ s

50 felle a- / il- (3,5-diochlorophenyl) -thiocarbamoyly-tüloeeBiii; ethyl esters, 5 parts alkylbene sulfonate as Hetsaittel and File diatomaceous earth is crushed and well mixed

the

a wettable powder that contains 50% active ingredient and is diluted with water before use.

Example 5 Production of an emulsifiable concentrate

10 parts of ^ - / M- (3,5-Diohlorphenyl) -thiocarbamoyloacy _- 7-'propion8äureäthyleeter, 80 parts of Diaethyleulfoxyd and 10 parts of a PoIyoxyäthylenphenylptienoläthers ala itaulgator are mixed well.

An emulsifiable concentrate is obtained which contains 10 % of the active ingredient

009825 / 212A

- Lasts 12 and the application gate is diluted with water

Example 6

Production of granules

5 steep M ~ (3 _r 5-dichlorophenyl) ^ cexl> aooyloxye8Big8äure _l 93 "5 parts clay and 1.5 parts polyvinyl alcohol as a binder" are reduced in size and well ashed. The obtained gene! Sch is kneaded IAIT water and granulated · gives granules, dme 5 i> active ingredient una be used as such scanning ·

Example 7

Production of a dusting agent »

2 parts of H- (5,5-Dichlorpiaenyl) -oarbamoylthioeßsigeäure, I ₁ 5 parts On-butyl-S-ethyl-S-benityldithiophbBphat, 0.1 part and 96.4 parts of clay are pulverized and mixed well. The result is a dust that contains 3.6 J * active ingredients and can be used as such »

Example 8 Manufacture of a dusting agent t

Z parts Oi - / »- {3 _r 5-I> ichiorphenyl J-CaTbSJBOyIoXxZ-PrOPiOnSaUTeä thy Ie et er, 1.5 parts On-Butyl-S-ä-üiyl-S-benaylditfciopüoephatr, 2 parts 0,0-Dimetiiyl ~ 0- (3-ffiethyl-4-nitrop4ienyl) ~ thiophoephate, 1.5 parts 3,4-ethylphenyl-H-methylcartoaoate and 93 ropes of ion are comminuted and mixed well. A stain remover containing 7 3 active ingredients is obtained and as such β can be used.

009825 / 212A

BATH ORIGINAL

1953A31

- "13 -

The following experiments illustrate the fungicidal effect of the erjTiiuiun ^ agQBtäOBto compounds of the general formula

Attempt 1

The seat compounds, which are present as a wettable powder, are diluted with enough water to achieve a concentration of O ₀ I #. Then roe plants sucked up to the three-leaved stage in dots of 9 ca diameter * were treated with the diluted solutions obtained (7 ml solution / pot ) * One day later the plants are infected with a spore suspension of Piricularia oryaae · 5 days later the number of diseased areas per 10 leaves is counted «Table III shows the results from which one can see; that the inventive compounds of the general formula X have a stronger fungicidal effect than the known compounds, soBo as ethyl (H-phenyloarbamoylthio) <- ee8ig8 acid ethyl ester.

Table III

ι connection Number of infected stel
len per 10 matter | m- (3 »5 ~ Diohlorpiienyl) - * oarbamoyl-
I ethyl thioacetate 19th b- (3 * 5 * »dichlorophenyl) -thiocarbamoyl-
I ethyl thioacetic acid ester 9 t ~ / k- (3,5-Mchlorplienyl) ~ thio ~
I car bcuBoyl oxy prop ion e acid
Ethyleeter 28 i- (3,5-Dichlorph # nyl) «cart> ai-oylthif> -
eesigsMuv 25th B-Phenyloarbaaoylthioöaeiiisäure-
ethyl ester 176 | untreated (cum comparison) 193

009825 / 2T2T

-u-

Varauoh 2

The Versuoiis connections, all dusts (concentration! 4.0 0 «W ₈ -Jt) la one dose τοη 100 ag j · pot applied to rice plants, which are up to * rierblsVttrlgen stages in pots τοη 9 ο «diameters were sucked« Linen will be the day later

tyslfsmü Heispflansea bit of a spore suspension τοη ftreh1l1if * Wlii * / infected «The number of infected sites is 3 Sag · spiLtsr counted, table IV shows the results from which you can see « It is true that the compounds of the general formula I according to the invention have a stronger fungicidal action than those known compounds, next as X-Phenyloarbaaoylthioeseigsäureäthylester and 0 ~ Xthyx-S, &> dipheuyldithiophospnat ·

Table IV

link Figure animal infected
Make i> ro sheet * - / k- (5 »5-ßiohlorphenyl) -carbaiaoyl-
oxyy-propioneäuxeätlij las ter 7 · 8 H- (3,5-dichlorophenyl) -oar bexaoylthio-
acetic acid ethyl ester 3.6 «- / H- (3,5-diehlophenyl) -thiocarba-
»Oyloxx7-propionic acid ether 6.5 N- (3 »5-diealorphenyl) -carbaaoyl-
oxyacetic acid 8.9 N- (3 f5-Sichlorpheny1) -carbamoy1-
thioeate acid 6.1 M-faenylparbamoylthioeselg-
ethyl acid ester 58.0 O-Xthy 1-S g S-diphenylüi tiiiophoephat 25.9 in treated (sum remaining) 61.7

009825/2124

BATH ORIGINAL

Attempt 3

The experimental connections were made as a wettable powder with water diluted to a concentration of 1.05C and in a quantity of 7 al per pot applied to KUrblspflänschen, which until now The 3- to 4-leaf stage was sucked in pots with a diameter of 12 cm. One lay later, the Fflänsohen with a Sprayed spore suspension of Sphaerotheca fuliginea. 10 saga later the infection emerges on the upper 4 leaves starirnt * The damage cage is created from the! »fixed surface calculated according to the following equation s

V (Infektionsinuex χ Number of Blattor) Damage & Bgrad - 4L χ IOC

Total number of sheets checked χ 5 The InfectionIndex is defined as follows}

Infected area of infection in ^ ex

no 0 small 1 middle 3 great 5

Table V shows the results from which it can be seen that the inventive compounds of general formula I. have a strong fungicidal effect, similar to that of one of the commercially available functi

009825 / 212A

BAD OBlGlNAl-

- 16 -Table V

link Sohäciigun & iigrad qr- / H- (3 »5-dichlorophenyl) ~ oarbanoyloxy_7-
propionic acid ethyl ether 3.8 H- (3,5-dichlorophenyl) carbamoylthio ~
esei _c e acid ethyl ester 1.6 H- (3,5-dichloropbenyl / -thiocarbaeoyl-
thioeeaigaauregthyleater 6.7 1 - / β- (3,5-dichlorophenyl) -thiocarbaaoyl-
oxx / propionic acid ethyl ether 8.6 I- (3 _P 5-W-chlorophenyl) -carbaaoyloxy-
acetic acid 5.9 I- (315-dichlorophenyl) -carb & moylthio ~
egg acid 3.7 H-Phenylcarbaaoylthioeeel ^ eäiirettthyleetfr 45.6 4,6-nitro-2- (l-a «thylheptyl) -phenyl-
orutonat 3.9 Unaffected (sun comparison) 41.3

Attempt 4

Several spots old oinee Duxciiiaeeser of 9 om w «rd« n sit iolcertrd · filled and 10 nl each infected with Pellioularia filaaentoea · potting soil is distributed on the surface. The Verettcheverbinuungea which can be formulated in advance are not diluted with β oriel s.aeser, so that a concentration of 0.05% is reached. The diluted solution (15 al LUBung / 3.3 ■) is then poured into the pots. After 2 hours there are 10 cucumbers & more sown. After 3 days, the condition of the infected seedlings is checked and the present portion of the stock is calculated according to the following equation

009825 / 212A

BATH ORIGINAL

Prosentation of the _m inventory

- 17 -

Number of healthy seedlings in treated pots

Number of ke idling θ in the tmb -

traded pots

χ 100

! Table VI increases the results, from which it is apparent that the compounds of the general erfindungsgemäsaen Porael I have a strong fungiside effect, which is equivalent to that of a commercially available in fungicidal agent (Pentachlornitrobensol) "Minimum,

Table VI

link Percentage dee
Inventory N- (3,5-dichlorophenyl) -carbaaoylthio-
ethyl acetate 93, β N- (3 _r 5-dichloroph & nyl) ~ thioaarbamoylthio-
acetic acid ethyl ester 100.0 df ^ {Ur- ( 3,5-dichlorophenyl J-thiocarbamoyloxjr / ·
ethyl propionate 90.2 N "(3,5-dichlorophenyl) -carbajaoyltlaioeeeige acid Ö9, l ü ~ Phenylcarl) aiaoylthioeQeigeäureäthyle8ter 0 Pentachloronitrobene sol ββ, 5 untreated (auo comparison) 0

009825/2124

Claims (1)

⁷ (D In which the radicals X mean halogen atoms, the radicals Y and Z are identical or different and represent oxygen or sulfur atoms, and the radicals R and R * are identical or different and Mean Waseereioffatome or lower alkyl radicals. 2 α K "(3 9 5-dichlorophenyl) -carbaooyloxyeasetic acid · 3 ο V- / N ~ (3 1 5 ~ /> chlorophenyl) -carbamoyloxy / -propionsättreäthylester. 4 ο o <- /) i- ( 3 1 5-dichlorophenyl) -thiocarbaaoylox ^ 7-propionic acid ethyl ester ₀ 5 ο K- (3 »5-dichlorophenyl) -carbeaoylthioeaetic acid. 6. N- (3f5-dichlorophyl) "carbaaoylthioacetic acid ethyl ester. 7 ° N- (3 »5-dichlorophenyl) ~ thiocarbaooylthioeacetic acid ethyl ester ° 009825/2124 BATH ORIGINAL - 19 - Process for the preparation of the compounds of the general formula Z according to Claim 1, characterized in that a 3 _? 5 ^ Dihalogenphenylieocyenat or -leothiocyenat of the general Jormel IX K «C-T (Π) in which the test X unö T has the meaning given in claim 1 have »With a compound of the general formula III HZ-CH-COOiI '(III) in which the radicals Z, R and H ^{1 have} the meaning given in claim 1, preferably in the presence of a catalytic amount of an organic base and / or an inert solvent. 9ο Use of the compounds according to claim 1 to θ as or in antimicrobial agents ₀ 009825/2124