CS239421B1 - 2-oxo-3-benzothiazolevinylmethylammonium salts and method of theier preparation - Google Patents

Description

The present invention relates to 2-Oxo-3-R-benzothiazolinylmethylammonium salts of general formula I

(I) where

R represents trlethylammonium, trbutylammonium, pyridinium, 3-methylpyridinium, 4-methylpyridinium, azochlnollnium, their method of preparation and their effect as plant growth stimulants.

Synthesis of 2-oxo-3-R-benzothiazolinylmethyl- _1- ethyl-propylammonium salt as a plant growth regulator has been addressed in the work (D'Amico JJ: USA Pat. 4,371,388 (1983); Chem. Abstr. 99, 22454 ( 1983)). The compounds were synthesized e.g. from 2-hydroxybenzothiazole and 1-chloro-2-dimethylaminoethane

+ Cl (CH ₂ ) _n N (CH ₃ ) _{2 nm} £ g _ C c = o (CH ₂ ) _n N (CH ₃ ) ₂ followed by alkyl halogenation (R 2) to

Rc-chloroV ⁰ Λ Γ toX-n (ch ₂ ) n (ch ₃ ) ₂

R = H, halogen; m = 0.2; η = 1 to 3; X 1 is halogen; R ^{@ 1} = alkyl, (un) substituted phenyl, halopyridinyl. In a variation of the dimethylemine group, piperldyl, morpholino and 4-alkylpiperazine were used. Further, structurally close, properly alkylated 2-oxo-3-benzothiasolinylmethylmethylamines were prepared by llannium reaction with 2-hydroxybenzothiazole. The conditions for the formation of mono and bia derivatives as well as their antimycocaterial and anti-viral effects have been studied (Holbová E., Sutoris V., Blockinger O .: Chem. Zvěsti 30, 195 (1976), Holbová E., Sidóová E., Odlerova 2: Chem. Rumors 30. 709 (1976); Holbova E., Odlerova 2 .; Chem. Rumors 34, 399 (1980); Holbova E., Odlerova 2., Rada B .: Heterocyeles 9, 1 503 (1976); 1978) Sutoris V., Šuolioliova Η., Holbova E., Rada B .: Chem. Zveeti 34, 700 (1980).

The same derivatives can be prepared from 3-chloromethyl-2-benzothiazolinone and primary amines (Stavrovakaja, V.I., Kolesova, M.O., 2nd C., Chim. 30, 689 (1960)).

The 2-oxo-3-H-benzothiazolinylmethylammonium salts of the present invention have not been described in the literature. A similar study of blological efficacy has not been addressed to date.

The process for the preparation of the compounds according to the invention is characterized in that 3-chloromethyl-2-benzothiazolinone

(II) reacts with a substance selected from the group consisting of trimethylamine, triethylamine, tributylamine, pyridine, 3-methylpyridine, 4-methylpyridine, isoquinoline in an organic solvent such as benzene, acetone, methylethylketone, methanol, dimethylformaldehyde to acetone 18 and acetone mixtures 80 ° C for 2 to 35 hours, the product being read by heating in gasoline and filtering off hot. The reaction is indicated by the following sehámas

where

R is as above.

Procedure for the preparation of 2-oxo-3-R-benzothiazolinylmethylammonium salts.

EXAMPLE

Preparation of 2-oxo-3-benzothiazolinylmethyl-triethylammonium chloride (II)

To 3.99 g (0.02 mol) of 3-chloromethyl-2-benzothiazolone, 10 ml of acetone and 5 ml of dimethylformamide was added 2.52 g (0.025 mol) of triethylaine. The reaction mixture was heated in a water bath at 40-50 ° C for 2 hours. The isolated crystalline solid was heated to boiling point in gasoline and filtered hot. Compounds III, IV and V were prepared in the same manner.

Example 2

Preparation of 2-oxo-3-benzothiazolinylmethyltributylammonium chloride (III)

5.99 g (0.03 mole) of 3-chloromethyl-2-benzothiazolinone, 5.55 g (0.03 mole) of tributylamine were dissolved in 25 ml of beneene, methyl ethyl ketone, or methanol, heated to the reaction mixture for 10 hours and 24 hours. hours at room temperature. The crystallized material was filtered off and the residue of unreacted 3-chloromethyl-2-benzothiazolone was extracted in the gasoline.

P r <k 1 and d 3

Preparation of 2- (2-oxo-3-benzothiazolinylmethyl) isoquinolinium chloride (VII)

A solution of 5.99 (0.03 mol) of 3-chloromethyl-2-benzothiazolinone, 5.55 g (0.035 mol) of isoquinoline, 15 ml of acetone and 5 ml of dimethylformamide was allowed to stand at room temperature for 35 hours. Crystalline material washed with warm benzene.

The elemental analysis and physicochemical constants of the synthesized compounds of the invention are shown in Table 1. 1 H-NMR spectra were recorded on a TESLA BS 487 A instrument at 80 MHz in deuterated trifluoroacetic acid, Internal Standard hexamethyldisoloxane. EU results in Table 2.

The water content of 2-oxo-3-benzothiazolinylmethylpyridinium chloride (IV) and 1- (2-oxo-3-benzotlazolinylmethyl) -3-methylpyridinium chloride (V) was determined by thermal analysis on a DERIVATOQRAPH type 00-102 from MOM, Budapest. System: E. Paulik, u. Paulir, L. Erdey.

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Table 2

¹ H-NMR chemical shifts (SS) of compounds synthesized according to the invention

number with I - K * <W ₃ 7.3 to 6.9 (ar, 4H, m)} 5.17 _(N-CH2, 2H, s) 3.20} (N ⁺ _-CH2, 6 H, m); 1.1 (CH 9H, m) II - 7.1 (ar, 4H, m) 5 5.20 _(N-CH2, 2H, s); 3.1 (N ⁺ -CH ₂ , 6H, m); 1.4 (CH ₂ , 6H, m); 0.90 (CH ₂ , 6H, m); 0.6 (CH ₃ , 9H, m) III -xo> 8.76 (H-2 &apos;, 6 &apos;, 2H, d); 8.27 (H-4 ', 1H, t); 7.79 (H-3', 5 ', 2H, t); 7.3 to 6.9 (ar, 4H, m); 6.41 _(N-CH2, 2H, s) IV / ^CH 3 8.54 (H-2,6 ', 2H, Si; 8.06 (H-4', 1H, d) {7.65 (H-5 ', 1H, t)) 6.40 (N-CH) _2, 2H, s), 2.21 _(CH3, 3H, s) in - <(C?> - CH 3 8.56 (H-2 &apos;, 6 &apos;, 2H, d); 7.56 (H-3 ', 5', 2H, d); 7.1 (ar, 4H, m); 6.40 _(N-CH2, 2H, s); 2.32 _(CH3, 3H, s) VI ies ° ® 9.63 (H-1 &apos;, 1H, s); 8.5 to 7.5 (H-3 ', -β', 6H, m); 7.4 to 6.8 (ar, 4H, m); 6.63 _(H-CH2, 2H, s)

s - single et, d - doublet, t - triplet, m - multiplet

The compounds of the invention are effective as plant growth promoters. Growth tests were performed by the authors modified method on the wolf object. Example 5 illustrates a method of testing the compounds of the invention for stimulatory and inhibitory activity.

Example 5

Semen gray wolves germinated in petri mills in a thermostate, in a thorn at 25 ° C. Germs after 48-hour growth were exposed in molar plants of 2-oxo-3-R-benzothiazolinylmethylammonium salts, where R is triethylammonium, tributylammonium, pyridinium, 3-methylpyridinium, 4-methylpyridinlum, isochlnolinium.

Testing ea performed 10 to 10 &lt; -1 &gt; mol.dm &lt; ³ &gt; in a concentration rock, and after 24 hours incubation, the increment of root extension was determined. A growth effect was also performed in the control sera for each assay. the width of the experimental and control groups, as well as the significance between the groups, were determined by blometrics.

Beta-indolylacetic acid (IAA) and 2,4-dichlorophenoxyacetic acid (2,4-D) were tested as standards. The results of the inhibitory effect of the synthesized compounds of the invention are shown in Table 3.

Table 3 (oA - ° ^Cl -

M- ₂ -ch ₂ -r

The stimulatory effect of the synthesized compounds of the invention

number R stimulation mol.drn ³ I - NCC 8 H 11 --j 2.85 10 ^-7 XI - n (c ₄ h ₉ ) ₃ 2.40 10 ' ³ III -In) CH · » 6.70 10 " IV 6.50 10 ⁷ in - ^ + 0) -0¾ 2.05 10 " VI - ⁺ © @ 3.00 10- ' ³ IAA 3.10 10 ' ² 2,4-D 4.95 10 ⁴

IAA - beta-indulylacetic acid 2,4-D - 2,4-diohlorophenoxyacetic acid

Claims (2)

OBJECT OF THE INVENTION 1. The 2-oxo-3-R-benzothiazolinylmethylammonium salts of the formula I SOJ_? ⁼ ° ¹ -N-CH ₂ -n Cl (I) where R represents triethylammonium, tributylammonium, pyrldinium, 3-methylpyridinium, 4-methylpyridinium, isoquinolinium. 2. A process according to claim 1, wherein the 3-chloromethyl-2-benzothiazolinone of formula II is: C = O Z1-CH-CI (II) reacts with a substance selected from the group consisting of triethylamine, tributylamine, pyridine, 3-methylpyridine, 4-methylpyridine, isoquinoline in organic solvents such as benzene, acetone, methyl ethyl ketone, methanol, mixtures of dimethylformamide and acetone at 18 to 80 ° C for 2 to 35 hours.