DEN0006104MA - - Google Patents

Description

FEDERAL REPUBLIC OF GERMANY

Registration date: September 20, 1952. Advertised on February 16, 1956

GERMAN PATENT OFFICE

PATENT APPLICATION

GROUP 451 CLASS 301

N 6104 IVa / 451

Johannes Thomas Hackmann and Willem Albertus Pel, Amsterdam

(Netherlands)

have been named as inventors

N. V. De Bataafsche Petroleum Maatschappij, The Hague

Representative: Dr.-Ing. F. Wuesthoff and Dr. F. Wuesthoff, patent attorneys, Munich 9

Treatment of plants to combat pathogens,

especially of mushrooms

The invention relates to the treatment of plants with certain isothiourea derivatives for the purpose of combating pathogens, especially fungi.

In the earlier patent (patent application

N 4949 IV a / 45 1) the applicant has already

X-

^R i

C = S or

N:

R,

suggested using isothiourea derivatives for such purposes, but it is to a different class of compounds than according to the invention.

The compounds claimed earlier are characterized by the general formulas 20

-SX or

N:
C-

R ₁

-SX

NR ₂

509 658/339

N 6104 IVa / 451

Here, X denotes an optionally substituted, preferably terminally halogenated, in particular chlorinated acyl group, Y either a hydrogen atom or an aryl group or a hydrocarbon radical which is optionally substituted, preferably terminally halogenated, in particular chlorinated, and R ₁ and R ₂ either hydrogen atoms or hydrocarbon radicals, which are optionally substituted, preferably terminally halogenated,

ίο in particular are chlorinated. The connections to be used should preferably be water-soluble.

In the German patent specification 705 106 is the use of isothioureas, which by a higher molecular weight cycloaliphatic radicals are substituted on the sulfur, or their salts as disinfectants claimed.

German Patent 715 541 describes the use of hydrohalic acid salts of substituted isothioureas for treating textiles in particular, for example as water repellants. The salts to be used according to this patent are obtained if thiourea or its derivatives, which can react in the isoform, are reacted with halomethyl compounds of the general formula RX-CH ₂ Hai or R ₁ X ₁ · CH ₂ Hai, where R is an aliphatic one , aliphatic-cycloaliphatic or aliphatic-aromatic radical with at least 11 carbon atoms, which can be substituted or contain O, S or N as a member in an aliphatic carbon chain or as a bridge member between the aliphatic and carbocyclic part of the radical. R ₁ denotes an alkyl radical which can be substituted, X denotes oxyphenyl, in which the hydroxyl group is in the ortho or para position to the CH ₂ Hai group, or

- CON < ^R2 or -0C0N < ^R2 or NHCON (^ ² ,

X ₁ -CON < ^R or -OCON < ^R , and R _{2 is} hydrogen

or alkyl, while Hal stands for halogen. The implementation can optionally in the presence of a. Solvent take place.

U.S. Patent 2,547,366 describes the use as fungicides and bacterialides of compounds the general formula

, NH

R - Phenyl- (OA) _n S - C:

• HX,

NHR '

where R is an alkyl group of 4 to 12 carbon atoms, R 'is hydrogen or alkyl groups having not more than 4 carbon atoms, A is an alkylene group having 2 to 3 carbon atoms, η is the numbers one to three and HX is an acid equivalent with an anion X. represents. U.S. Patent 2,557,633 describes the use of acetylaminophenylsulfonyl-S-alkylisothioureas of the general formula

CH ₃ C-NH-C ₆ H ₄ -SO ₂ -NC-SR,

H NH,

where R is a lower alkyl radical, as chemotherapeutic agents.

The compounds to be used according to the invention do not belong to any of the subclasses of isothioureas to borrow according to the German application cited above and the USA patents Purposes and / or are to be used in a similar way.

According to the present invention, for the control of pests, and of plant pathogens, in particular of fungi and / or bacteria S-alkylisothiourea derivatives of the general formula

NH ₂

C = NH

S —R

where R is an optionally substituted alkyl group with ι to 16 carbon atoms, and salts thereof, in particular HCl, HBr or H ₃ PO ₄ salts, are used.

The compounds mentioned can be used, for example, for treating animals or of materials that run the risk of being attacked by fungi and / or bacteria. In particular but they are suitable for the treatment of plants.

While the pesticides previously used against fungi or plant pathogens ι oo the action against the various fungi and bacteria is generally very unevenly strong and also depends on the circumstances, for example on the type of animals, materials or plants on which the fungi live , it has been found that the substances to be used according to the invention have a surprisingly low specificity in their action. It goes without saying that this is of the greatest practical importance, because it is more economical if one can use the same means over and over again in different cases than if one needs a large store with many specifically effective means. The hydrogen bromide salts of Sn-octylisothiourea and of Sn-heptylisothiourea have proven to be particularly successful. Phytophthora on tomatoes e.g. B. could not be higher than 0.05 weight percent to 86 ° / ₀ suppressed, which was not possible with any of the usual in practice against the disease agent with aqueous solutions of these substances in concentrations. ' _Λ >"

The substances to be used according to the invention can either be used individually or in combination with one another or used with other fungitoxic, viritoxic, insecticidal or acaricidal substances whose effect can be an internal or an external one, whereby wetting agents and given

658/339

N 6104 IVa / 451

if adhesives can also be added. Also combinations with plant nutrients and or or plant hormones are possible.

Although the substances to be used according to the invention can be administered in any conventional manner, spraying the plants to be treated is particularly preferred. Also by dusting with solid powder-like preparations may give good results.

ίο When spraying come preferably either aqueous or oily solutions of the active substances with a content of ο, οΐ to ι percent by weight, preferably from 0.05 to 0.5 weight percent of these materials for use, with about 1000 liters per hectare are to be sprayed. The spraying takes place under If much smaller amounts of liquid are used, higher concentrations should be used will. If the plants to be treated with their roots in a solution according to the invention substances used are immersed, which is particularly recommended for the treatment of Cucurbitäcaeen far lower concentrations can be used, preferably those from 0.01 to 0.05 Weight percent. In this case, the duration of treatment should extend to a few hours.

Of course, the compounds to be used according to the invention do not need to be used from the start to be present in pure form, according to the invention in the form of solutions or any other Preparations to be applied. The presence. of inactive admixtures that are used in the technical Production have arisen, is generally not disadvantageous. Mixtures of active substances can also be used Use connections that can easily be made from technical products.

The effectiveness of the plant protection agents to be used according to the invention relates to how mentioned, on very different kinds of pathogens, including those mentioned in the above older patent ...... (application N 4949 IVa / 451) the applicant of their large practical Importance due to be specially listed.

Although the compounds to be used according to the invention are those according to the earlier patent

(Application N 4949 IVa / 451) are closely related to the use, a systemic effect in plants, that is to say an effect from the inside of the plants, could often not be demonstrated. Presumably, the substances only have an effect in many cases where they have been applied to the plants to be treated.
The invention is illustrated by the following examples, which are not to be interpreted as restrictive.

Example I.

Concentrations from 0.05 to 0.15 percent by weight

' an aqueous solution of the HBr salt of Sn-octylisothiourea were investigated against Colleto-

■ 60 trichum and rust on beans, rust on rye and Phytophthora infestans on potatoes as well Tomatoes. Some of the results of these studies are given in Table I below.

The degree of suppression used in this and the following examples as a measure of the effectiveness of the Substances specified was found by looking at the ratio of those attacked by the disease Leaf surface determined from the total leaf surface in treated and untreated plants and subtracted the quotient of these two numbers from 1. The size so obtained is, in percent expressed, the degree of suppression. The point in time at which the determination of the degree of suppression, as just defined and stated, it was chosen in each case in such a way that all those who remained untreated infected Plants showed distinct symptoms of the disease.

The leaf surfaces were usually not measured, but estimated with the required accuracy. In this way, a trained person can determine the degree of suppression with an accuracy of about 5 ° / _0. This accuracy is sufficient, since in general the results obtained in biological experiments can only be reproduced within fairly wide limits.

table I. Under-
depressive
Degree
in percent illness plant Applied
Conc
tration in
Weight
percent 60
.92
. 95
80
.86
100 Colletotrichum
rust
rust
Phytophthora
Phytophthora
Phytophthora Beans
Beans
rye
potatoes
tomatoes
tomatoes 0.1
0.1
0.5
0.1
0.05
0.1

Example II

Aqueous solutions of the HBr and H ₃ PO ₄ salts of Sn-heptylisothiourea, Sn-octylisothiourea, Sn-decylisothiourea and S-cetylisothiourea were examined for comparison purposes in concentrations of 0.1 and 0.3 percent by weight against Phytophthora on potatoes by 2 month old infected plants were sprayed with the aqueous solutions and after a certain time determined the degree of suppression. The results are given in Table II.

Table II

connection Appointment
was enough
Conc
tration in
Weight
percent Under-
press
k-
degree in
percent HBr-SaIz from Sn-Heptylisothio
urea 0.1
0.3
0.1 60
72
58 HBr-SaIz from Sn-Heptylisothio
urea HgPO ₄ salt from Sn-Heptyliso
thiourea

509 658/339

N 6104 IVa / 451

(Continuation of Table II)

connection Appointment
was enough
Conc
tration in
Weight
percent Under-
push
k-
degree in
percent HBr salt of Sn-Octylisothio-
urea
HBr salt from Sn-Octylisothio
urea
H ₃ PO ₄ salt of Sn-Octyliso-
thiourea
HBr-SaIz of Sn-Decylisothio-
urea
HBr-SaIz of Sn-Decylisothio-
urea
H ₃ PO ₄ salt of Sn-decylisothio-
urea
H Br salt of S-cetyliso thiourine
material 0.1
o, 3
0.1
0.1
0.3
0.1
0.1
0.3
0.1
0.1 66
82
56
56
76
58
14th
34
0
46 HBr salt of S-cetylisourea
H ₃ PO ₄ salt of S-cetylisothio-
urea
Cu oxychloride

Example III

Celery plants attacked by Septoria were sprayed with aqueous solutions of 0.1 and 0.3 percent by weight, respectively, of the H ₈ PO ₄ salt of Sn-heptylisothiourea. No phytotoxicity occurred and the degree of suppression achieved was 48 and 46%, respectively. ■, ■

Claims (4)

Patent claims: i. Use of S-alkylisothiourea derivatives the general formula NH ₂ C = NH S —R wherein R is an optionally substituted alkyl radical with 1 to 16, preferably up to 12 carbon atoms represents, for the treatment of plants for the purpose of combating pathogens, in particular · Of mushrooms. 2. Use of S-alkylisothiourea derivatives according to claim 1, characterized in that S-alkylisothiourea derivatives are used in the form of their salts, in particular their HBr, HCl or H ₃ PO ₄ salts. 3. Use of substances according to claim 1 or 2, characterized in that the substances in aqueous solutions, especially in concentrations of 0.01 to ι percent by weight, preferably of 0.05 to 0.5 percent by weight administered, preferably by injection. 4. Use of substances according to claim 1 or 2, characterized in that the root system of the plants to be treated, especially of Cucurbitacaeen, in one for a few hours 0.01 to 0.05 weight percent solution of the substances according to the invention is immersed. © 509 658/339 2.56