DE1812966B1 - 2-Amino-azacyclotridecenes and their use as fungicides - Google Patents

Description

2-Amino-azacyclotridecene of the general formula I act to grow, occur, to combat or

_{Dam the NHR} , especially because the 2-amino-azacyclo-

'tridecene of the formula I also act as systemic fungicides

(I) can. Furthermore, the inventive active

5 substances for the treatment of seeds and the soil

can be used.

wherein R is an alkyl radical having 1 to 14 carbon atoms. The fungicidal effectiveness of the invention

men, the cyclohexyl, the benzyl or phenylethyl usable 2-Ammo-azacyclotridecen derivative residue means, and their salts with inorganic and linge was determined on the basis of the following experiments organic acids have been used in the fight against and with from the French patent proved superior by mushrooms. 1 367 799 known compounds that

These 2-amino-azacyclotridecenes are prepared, hereinafter referred to with an asterisk, verindem one azacyclotridecan-2-one with triethyloxo- like.

nium boron tetrafluoride in 2-ethoxy-azacyclotridecen- (l) The effect is assessed according to the following scale:

transferred and this with an amino compound of * 5

general formula II 10 = ineffective, same infestation as untreated

R-NH ₂ (II) control plants,

9 to 1 = infestation reduction after linear decrease

in which R the meanings given under formula I estimate,

has, implements and, if necessary, the received re-20 _ '

Action products with inorganic or organic ° ^{= kem Be: ta11}

Acids converted into their acid addition salts. It is

advantageous the reactions _{according to} the invention in active alternaria solani on tomatoes

solution inert to the reactants (Solanum lycopersicum)

or diluents, such as aliphatic and aro- 25 each *

matic halogenated hydrocarbons, e.g. B. Methy tomatoes of the "Lukullus" variety are

Lene chloride, chloroform, chlorobenzene, or aroma up to four weeks of cultivation in the greenhouse with the table hydrocarbons, z. B. benzene, toluene, test substance in the form of a spray liquor (concentrated xylenes, or ethers and ethereal compounds tration 0.1% active ingredient) to be carried out to runoff. The reaction of the 2-ethoxy spray 3 ° and after the spray coating has dried on, the bond with the amine of the formula II is advantageously carried out with a standardized spore suspension of the fungus in the presence of a tertiary amine. As infected. After about 5tägigem stay in humid tertiary amines, for example, come trimethylamine, atmosphere at about 22 ⁰ C, small triethylamine, Triäthanoiamin, pyridine develop into consideration. black spots of infection on the leaves. In the reaction, the ethoxy group is split off with the formation of 35 evaluation basis for the experiment and the number of stains from the group. - NHR replaced.

The acid addition salts are obtained by adding equivalent amounts of a 2-amino-azacyclotridecene the general formula and one ent- 4 °

speaking inorganic or organic acid in

Presence of one of the reactants 2-methylamino-azacyclotridecene (l) inert solvent or diluent. 2-ethylamino-azacyclotridecene (l). As inorganic acids, for example, the 2-octvlamino-azacyclotridecene (D

Active ingredient

Infestation intensity

2 3 1 2 2 10 10

the following: hydrogen halides, nitric 45 2-decylamino-azacyclotridecen- (l)

acid, sulfuric acid, phosphoric acids, and as orga- 2-dodecylamino-azacyclotridecen- (l) ...

Niche acids: formic acid, acetic acid, propion- 2-dodecylamino-azacyclohepten- (l) * ...

acid, lauric acid, myristic acid, palmitic acid, 2-decylamino-azacyclohepten- (l) *

Stearic acid, sorbic acid, oxalic acid, succinic acid,

Glutaric acid, adipic acid, sebacic acid, benzoic acid, 5 ° toluenesulfonic acids, naphthoic acid, phthalic acid, etc.

As a result of low toxicity for warm-blooded animals and poor _effect against Botrytis cinerea on Vicia faba

Lender phytotoxicity m the practical application <= <= <= fc _au b _o hneri) concentrations, which related between 0.01 and 2% »

on the active ingredient, the compounds of the 55 In Petri dishes, which are specially designed for plants with moistened filter paper, general formula I, three well-developed, equally suitable for protection. They work, for example, against real large leaves of Vicia faba, which are made from powdery mildew, such as cucumber powdery mildew (Erysiphe cichora - an active ingredient hercearum formulated as a wettable powder) and rose powdery mildew (Sphaerotheca pannosa); The broth (0.1% active ingredient) made dripping wet against powdery mildew fungi, as the pathogens of the herb 60 are sprayed. After the spray and tuber rot of the potatoes (Phytophtorainfestans) has dried off; They are coated with a freshly prepared spore against leaf spot pathogens such as Alternaria solani; infected against suspension of the fungus. After the sheets rusts, as have been held bean rust (Uromyces app.), Further 1 or 2 days in a humid atmosphere at 18 to 2O ⁰ C against particularly difficult combated gray to show up on the leaves mold (Botrytis cinerea). By applying 65 black, initially point-like spots, it is possible to prevent fungal infections, which spread rapidly to plants. The number and size of the infection and plant parts (fruits, flowers, foliage, are used as an assessment standard for the active stems) and on plant parts that only appear after the test substance has been isolated.

Active ingredient

Infestation intensity

2-Octylamino-azacyclotridecene (1) 2

2-decylamino-azacyclotridecene (l) 5

2-dodecylamino-azacyclotridecen- (l) .... 2 2-dodecylamino-azacyclohepten- (l) *

Effect on Uromyces appendiculatur (bean rust) on beans (Phaseolus vulgaris)

Bean plants in the two-leaf stage are sprayed to runoff point with a suspension of the substances formulated as wettable powder (concentration of the suspension 0.1% active substance). After drying the spray coating, the plants are sprayed with a fresh spore suspension of bean rust infected (five plants per product) and then kept for 1 day in a humid chamber, then in a greenhouse at 20 to 22 ⁰ C. The evaluation of the experiment is based on the number of rust pustules present after about 8 to 12 days.

Active ingredient

2-n-Butylamino-azacyclotridecen- (l) 2-Decylamino-azacyclotridecen- (l) .. 2-Benzylamino-azacyclotridecene (1). 2-dodecylamino-azacyclohepten- (l) * 2-decylamino-5-tert-butyl-azacyclohepten- (l) *

Infestation intensity

10

In the following examples, the temperatures are given in degrees Celsius.

example 1

a) 114 g Triäthyloxom'um-boretetrafluoride (manufactured according to EMeerwein, J. Prakt. Chem., 154,

S. 120 [1939]) dissolved in 300 ml of anhydrous methylene chloride are at 25 to 30 ° dropwise with a A solution of 99 g of azacyclotridecan-2-one in 300 ml of anhydrous methylene chloride is added. After the addition has ended, the reaction mixture is at for 12 hours

ίο room temperature and stirred, then cooled to 0 to 5 ° and treated with 100 ml of a 50% strength aqueous potassium carbonate solution ^s. The methylene chloride phase is separated off, washed with water and dried, and the methylene chloride is distilled off. Of the

Residue - · 2-ethoxy-azacyclotridecen- (l) - · has the boiling point 92 to 96 ° at 0.05 torr.

b) 57 g of 2-ethoxy-azacyclotridecene (l) are mixed with 46.5 g of dodecylamine, 3 ml of triethylamine in 300 ml dissolved anhydrous benzene and taking 16 hours

ao refluxed. The benzene is then distilled off and the residue is fractionated. The 2-dodecylaminoazacyclotridecen- (l) has a boiling point of 185 to 188 ° at 0.01 Torr.

Example 2

7.25 g of 2-dodecylamino-azacyclotridecene (l) and 4.0 g of lauric acid are dissolved in 30 ml of absolute ethanol dissolved in the warmth. The alcohol is then distilled off in vacuo. The oily residue will crystalline when standing. The 2-dodecylamino-azacyclotridecen- (l) -laurinate After recrystallization from ethyl acetate, it has a melting point of 53 to 55 °.

In the ways described in Example 1, using equimolar amounts of 2-Äthoxyazacyclotridecen-CO and the corresponding amine, the compounds summarized in the table below are also prepared.

link

boiling point

Melting point

2-methylamino-azacyclotridecen- (l)

2-ethylamino-azacyclotridecen- (l)

2-isopropylamino-azacyclotridecene (l)

2-n-butylamino-azacyclotridecen- (l)

2-hexylamino-azacyclotridecen- (l)

2-octylamino-azacyclotridecen- (l)

2-dodecylamino-azacyclotridecene (1) hydrochloride

2-dodecylamino-azacyclotridecene (1) nitrate

2-tetradecylamino-azacyclotridecen- (l)

2- / S-dodecylaminoethylamino-azacyclotridecene (1).

2-benzylamino-azacyclotridecene (l)

2-Phenäthylamino-azacyclotridecen- (l)

2-Cyclohexylamino-azacyclotridecen- (l)

2-tetradecylamino-azacyclotridecene (1) perchlorate. 2-Tetradecylamino-azacyclotridecen- (l) -laurinate ... 2-Tetradecylamino-azacyclotridecen- (l) -oxalate ....

** Molecular distillation.

72 to 74 ^o / 0.01 torr

80 to 82 ° / 0.03 torr

92 to 9570.02 torr

109 to 11270.02 torr

130 to 13,370.03 torr

172 to 17,570.03 torr

oil

oil

2007 0.01 Torr **
150 to 15 171.00 torr
132 to 13670.02 torr
168 to 17,470.01 torr

42 to 43 °
42 to 44 °

84 to 86 ^a

62 to 64 °

53 to 56 °

116 to 120 °

The 2-amino-azacyclotridecenes of the general formula are known per se for use in Way processed into solid or liquid means.

Claims (5)

Patent claims: 1. 2-Amino-azacyclotridecene Formula I of the general UN NH - R in which R is an alkyl radical with 1 to 14 carbon atoms, the cyclohexyl, benzyl or phenyl 5 6 means ethyl radical, and their acid addition salts 6. 2-tetradecylamino-azacyclotridecen- (l) -lauri- with inorganic and organic acids. nat. 2. 2-methylamino-azacyclotridecene (I). 7. 2-Benzylamino-azacyclotridecene (I). 3. 2-Octylamino-azacyclotridecene (I). 8. The use of the compounds according to 4. 2-decylamino-azacyclotridecene (I). 5 claim 1 for prevention and suppression 5. 2-Dodecylamino-azacyclotridecene (I). of fungal growth on plants and parts of plants