Trans-4-azido-3,6-dimethyloxazolidine-2-tion, showing nematocidal activity

 

(57) Abstract:

Usage: agriculture as a substance exhibiting nematocidal activity. The inventive product: TRANS-4-azido-3,6-dimethyltetrahydrofuran-2-tion - C6H11N5S. Output 89,5 of 97.8% so pl. 126,5 of 127.5C. Reagent 1: 4-hydroxy-3,6-dimethyl-hexahydropyridine-2-tion. Reagent 2: sodium azide. Reaction conditions: concentrated hydrochloric acid, 20C. table 3.

The invention relates to a new derived hexahydropirimidine series, namely TRANS-4-azido-3,6-dimethylhexylamine - midin-2-tion of formula I, manifesting nematocidal activity and which may find application in agriculture.

I

The closest structural analogues of the proposed compounds are 2-mono - and 2,4-bifunktionalno substituted hexahydropyridine.

However, information about the use of these compounds in agriculture is rather limited. So, [1] it is shown that the hexahydropirimidine series-2-ones of the formula II are beneficial to the growth of marine algae

II There is evidence that 4-functionally substituted 3-aryl(hetaryl)hexahydropirimidine series-2-ones (III) are herbicide activity [2, 3]

III
the trade substituted aromatic pyrimidine [4] however, information about nematocidal activity of functionally substituted pyrimidines as aromatic and hydrogenated, which are structural analogues of the claimed compounds are not detected.

The closest to the nature of the activity, but very far on the chemical structure of the compound (I) are heteropus, Etats, carnation used in agriculture as nematicides, in particular against alprazolaj nematodes, rice aphelenchoidea, rot nematode of potatoes, sugar beet cyst nematodes and root-knot nematodes in the soil. These compounds, selected as a prototype, have the following disadvantages.

Heteropus-O-phenyl-O-ethyl-S-propertiesthat and Etats-O-ethyl-ethylpropyl-O-(2,4-dichlorophenyl)thiophosphate belongs to a class of phosphorus-containing substances have smell and high acute toxicity (for example, heterophase LD50-30-60 mg/kg in rats), which significantly reduces their practical value.

Carnation-dihydrate N-methyldithiocarbamate sodium toxic (LD50= 146 mg/kg in mice), are inconvenient to use, as released during decomposition methylisothiocyanate irritates the mucous membranes of the eyes, polycarpos new effective low-toxic, available nematicides is a very important task.

The purpose of the invention to provide new derivatives of the hexahydropirimidine series-2-thione with a higher nematocidal activity compared with used in agriculture products.

The goal achieved by a synthesis of previously undescribed compound TRANS-4-azido-3,6-dimethyloxazolidine-2-thione (I) having a high nematocidal activity against alprazolaj nematodes, rice aphelenchoidea, rot nematode of potatoes, sugar beet cyst nematode, as well as against root-knot nematodes in the soil.

Synthesis of compound (I) was carried out by the reaction of nucleophilic substitution of hydroxyl group in the available TRANS-4-hydroxy-3,6-dimethylhexane - pyrimidine-2-tione (IV) [5] on the azide group in the interaction of the compound (IV) with sodium azide and hydrochloric acid in the aquatic environment. To complete the reaction at 20aboutSince it takes about 24 h, the yield of the product of synthesis is 95-98% by increasing the reaction temperature, the rate of formation of compound (I) increases, however, decreases the product yield of the reaction. So, at a temperature of 70aboutWith and lie
+ NaN3+HCl

The method of obtaining the compound (I) is clear from examples 1-3.

P R I m e R 1. Synthesis of TRANS-4-azido-3,6 - dimethyloxazolidine-2-thione at 20aboutC.

To a cooled to 0aboutWith a mixture 10,10 g (63.1 mmol) of finely ground hydroxypyrimidine (IV) of 7.00 g (to 107.7 mmol) of sodium azide and 20 ml of water, add cooled to the same temperature a solution of 9.3 ml (108,4 mmol) of concentrated hydrochloric acid in 25 ml of water. The resulting mixture is left in a closed container at 20aboutWith 92 hours, occasionally shaking the contents. Cooled to 0aboutC, the precipitate is filtered off, washed thoroughly with ice water, dried. Get 11,42 g (97.8 per cent) is almost pure compound (I).

P R I m m e R 2. Synthesis of compound (I) at 70aboutC.

Receive the procedure described in example 1, from 0,548 g (3,42 mmol) hydroxypyrimidine (IV), 0,379 g (of 5.84 mmol) of sodium azide, and 0.50 ml (5.83 mmol) conc. hydrochloric acid, 2.4 ml of water, however, the reaction is carried out at 70aboutC for 10 minutes Yield compound (I) is 0,567 g (89.5 per cent).

P R I m e R 3. Synthesis of compound (I) if 50aboutC.

Receive the procedure described in example 1, from 0,473 g (2,95 mmol) hydroxypyrimidine (IV) 0,330 g (5.08 mmol) of the azide nchod the compound (I) is 0,499 g (91,4%).

The compound (I) is purified by recrystallization from ethyl acetate. So pl. 126,5-127,5aboutWith (decomposition; from ethyl acetate).

Found, 39,44; N. Of 5.75; N 37,84; S 17.11 Per Bbl. WITH6H11N5S. Calculated With 38,90; N. Of 5.99; N 37,81; S 17,31.

UV-spectrum (in acetonitrile),maxnm (lg): 214 (4,11), 257 (4,27).

IR-spectrum (in mineral oil), <N>nu<N> cm-1: 3208 Shire. (<N>nu<N> NH), 2103 (N3), 1525 and 1501 (thioamide-II).

Range PMR (DMSO-D6), , M. D. charged 8.52 S. of user. (NH, JNH,6-HAbout Hz, JNH,5-He1.5 Hz), 5,39 D. D. (4, J4E,5e=2.3 Hz, J4E,5A=3.5 Hz), 3.45 m (6, J5e,6A= 3.8 Hz), 3,35 C (N-CN3), 2.09 m (5, J5e,5A=a 13.9 Hz), 1.70 to DDD (5, J5A,6A=and 12.2 Hz), 1,15 d (6-CH3I , JCH3,6-=6,5 Hz).

The compound (I) is a white crystalline substance, insoluble in water, ether, hexane, poorly soluble in cold ethyl acetate, soluble in acetone, acetonitrile, dimethylformamide, dimethyl sulfoxide. Stable when stored.

The structure of compound (I) clearly proved by IR, UV and PMR spectroscopy.

Coreena group of compound (I) is in the UV spectrum by the presence of intense absorption band at 214 and 257 nm, and the IR spectrum bands "tio the th group in the molecules of the compound (I) leads to the presence in the IR spectra of this compound is very intense absorption band at 2103 cm-1.

Method PMR spectroscopy established that the compound (I) is formed completely diastereoselective in the form of individual transisomer. On the basis of the constants of spin-spin interaction of the protons of the N-H, 4-H, 5-H and 6-H shows that the molecules of this compound are in krestovinoy conformation with axillae orientation of the azide group at the atom WITH(4)and Equatorial orientation of the methyl group at the carbon atom WITH(6).

The method of determining nematocidal activity of compound (I) and the obtained results are shown in the examples 4, 5.

P R I m e R 4. Test compounds (I) on nematocidal activity against alprazolaj nematode, stem nematode of potatoes, rice aphelenchoidea, beet cyst nematodes.

In laboratory conditions tested compounds on the toxicity towards alprazolaj nematode Panagrellus redivivus, stem nematode of potatoes Ditylenchus destructor, rice aphelenchoides Aphelenchoides besseyi, beet cyst nematode Heterodera schachtii.

Sproting, stableboy the nematode of potatoes and rice aphelenchoides were cultured in the laboratory, larvae of beet cyst nematodes kind of is, the C which way dilution got a working solution of a given concentration. The activity of the compounds was studied by immersing the suspension of nematodes in the working solutions of the compounds. Progress is the following: in a Cup with a capacity of 1.5 ml poured into 0.5 ml of distilled water, was placed there nematodes in the amount of 30-40 pieces Then each Cup was added to 0.5 ml of the working solution of specified concentration. In the control cups were added to 0.5 ml of distilled water. Then the cups were placed in a humid chamber Petri dishes with moistened filter and placed in a thermostat (25-27aboutC). The counts in experiments conducted in 48, 120 and 168 h by counting under a binocular microscope, living and dead nematodes.

As can be seen from the table. 2, the compound (I) showed high activity against rice aphelenchoidea this ratio at a concentration of 0,0033% D. N. surpassed atafo (94,8% and 81.8 percent, respectively). The compound (I) showed also high nematocidal activity against rot nematode of potatoes, and this activity was higher (at a concentration of 0,0011% D. N.) or on the level of activity of atafona. In addition, compound (I) in a concentration of 0.02% D. N. showed a slightly higher nematocidal activity against St. IGNOU activity against root-knot nematodes in the soil. Vegetation tested against root-knot nematodes was performed by adding the compound (I) in soil infested with the larvae of root-knot nematodes Meloidogyne incognita and M. arenaria, uniform mixing for 5 days before sowing culture of cucumber. The compound (I) was tested in the form of sand granules prepared from 30 g of the granulate and 4% stock solution of the compound (I). Evaluation of biological efficacy was performed 25 days after sowing to reduce galloroman on the roots compared to control.

The percentage reduction in galloroman and death of nematodes was calculated by the formula:

T 100 where the total number of nematodes, the average number of galls in the control variant;

in the number of live nematodes, the average number of galls in a test version.

Assessment of the activity of the compounds was performed according to the percentage reduction in galloroman.

As can be seen from the table. 3, the compound (I) if the consumption rate to 0.032 g/kg soil reduce haloorange greater than that used in agriculture heteropus (69,5% and 65.2 percent, respectively).

Thus TRANS-4-azido-3,6-dimethyloxazolidine-2 - tion (I) showed high biological efficacy against alprazolaj nematodes, rice aphelenchoides activity of compound (I) was comparable, and in some cases exceeded the activity used in agriculture products.

Given the need for replacement of nematicides heteropoda, Etats and carnation due to their high toxicity and difficulty in handling, you should consider the claimed compound (I) having a high nematocidal activity, and obtained with a high yield based on the available cheap domestic raw materials, which are promising for applications in agriculture as nematocides of the drug.

TRANS-4-azido-3,6-dimethyloxazolidine-2-tion formula

< / BR>
showing nematocidal activity.

 

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