CS265759B1 - 2- (2-Furylvinylene) -3-substituted benzothiazolium salts and methods for their preparation - Google Patents

Abstract

The solution falling within the field of chemistry and agriculture relates to new 2-(2- -furylvinylene)-3-substituted benzothiazole salts, of the general formula A, where R means hydrogen and X- means HSO4 or R means methyl and X" means J", CIO4 or BF4 or R means benzyl and X" means Br", CIO4, BF4 or NO3 or R means allyl, propargyl, carboxymethyl, methoxylcarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, vinyloxycarbonylmethyl, allyloxycarbonylmethyl or benzyloxycarbonylmethyl and X" means Br", methods of their preparation and their use. The substances mentioned serve as plant growth regulators.

Description

The invention relates to 2-[2-furylvinylene]-3-substituted benzothiazole salts of general formula A

where

R is hydrogen and

X ^- means HSO ₄ or

R is methyl and X is J, ClO^ or BF^ or

R is benzyl and X is Br, ClO, BF or NO or

R means allyl, propargyl, carboxymethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, vinyloxycarbonylmethyl, allyloxycarbonylmethyl, or benzyloxycarbonylmethyl and X means Br ^- and methods of their preparation.

Until now, the synthesis of 2-/2-furylvinylene/-3-substituted benzothiazole salts according to the invention has not been given attention and is not described in the literature. The syntheses were carried out within the framework of the study of the structure of benzothiazole salts and some of their biological effects. Good results have been achieved in the field of directed dedifferentiation transformation of leguminous plants (Sekerka V., Sutoris, V.: AO 231 241; Sekerka V., Sutoris V.: AO 321 242) in the regulation of the growth of antimicrobial activity (Sutoris V., Halgaš J., Sekerka V., Foltínová P. , Gápolovský A.: Chem. zvěsti 37 (5), 653 (1983); Halgaš, J., Sutoris V., Foltínová P., Sekerka V.:

Chem. zvesti 36 (6), 799 (1983); Foltínová P., Sutoris V., Sodomová J., Halgaš J.: Biológia (Bratislava) 38, 7, 671 (1983); Sutoris V., Gáplovský A., Schlerová R., Sekerka V.: Chem. zvesti 39 (4), 491 (1985) and in the field of increasing sugar content in sugar-producing plants (Sutoris V., Sekerka V., Halgaš J., Bajči P.: AO 237 706).

The synthesis of the starting 2-(2-furylvinylene)benzothiazole was carried out by condensation of 2-methylbenzothiazole with furylaldehyde according to Dryanska V. and Ivanov G. (Dryanska V., Ivanov C.: Dokl. Akad. Nauk, Bolg. 23 (19), 1 227 (1970)). 2-(2-furylvinylene)-3-substituted salts were prepared by the action of alkyl halides on 2-(2-furylvinylene)benzothiazole. Further, by exchange of the halide anion in 2-(2-furylvinylene)-3-substituted salts with perchlorate, tetrafluoroborate, nitrate and by the action of H ₂ SO ₄ on 2-(2-furylvinylene)benzothiazole to form 2-(2-furylvinylene)benzothiazole to form 2-(2-furylvinylene)benzothiazole to form 2-(2-furylvinylene)benzothiazole hydrosulfate.

The essence of the method for preparing 2-(2-furylvinylene)benzothiazolium sulfate according to the invention is that 2-(2-furylvinylene)benzothiazole of the formula B

/B/ is treated with sulfuric acid in an anhydrous ketone or tetrahydrofuran environment.

The essence of the method for preparing 2-(2-furylvinylene)-3-methylbenzothiazolium iodide according to the invention consists in treating the substance of formula B with methyl iodide in an environment of anhydrous acetone, tetrahydrofuran or acetonitrile.

The essence of the method for preparing compounds of the general formula A, where R represents allyl, propargyl, benzyl, carboxymethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, vinyloxycarbonylmethyl, allyloxycarbonylmethyl, benzyloxycarbonylmethyl and X represents bromine, consists in treating the substance of the formula B with a compound of the general formula RBr has the meaning given in this point^ in acetonitrile or tetrahydrofuran environment.

The essence of the method for preparing compounds of general formula A, where R is methyl and X ^- represents ClO^ or BF^, consists in treating 2-(2-furylvinylene)-3-methylbenzothiazolium iodide with a compound of general formula MeX^, where Me represents sodium or potassium and X^ represents ClO^ or BF^ in a methanol medium.

The essence of the method for preparing compounds of general formula A, where R is benzyl and X ^- represents ClO^ or BF^, consists in treating 2-(2-furylvinylene)-3-benzothiazolium bromide with a compound of general formula MeX^, where Me and X^ have the above-mentioned meanings in methanol.

The essence of the method for preparing 2-(2-furylvinylene)-3-benzothiazolium nitrate of general formula A consists in treating 2-(2-furylvinylene)-3-benzylbenzothiazolium bromide with a compound of general formula MeNO 3 , where Me has the above-mentioned meaning in methanol.

Methods for quaternization of 2-(2-furylvinylene)benzothiazole

Example

2-(2-furylvinylene)benzothiazolium hydrosulfate

To 0.01 mol of 2-(2-furylvinylene)benzothiazole in 15 cm of anhydrous acetone or tetrahydrofuran was added dropwise with stirring 0.015 mol of sulfuric acid diluted in 5 cm of acetone or tetrahydrofuran. After 2 h the crystalline portion was washed with acetone and crystallized from methanol. M.p. 184-187, yield 42%. For ^c i3 ^H n ^NO 5 ^S 2 ^h 325, ³⁷ calculated % C = 47.98, % H = 3.40, % N = 3.99, % S = 19.70. Found % C = 48.27, % H = 3.47, % N = 4.00, % S = 19.48.

Example 2

2-(2-Furylvinylene)-3-methylbenzothiazolium iodide

0.01 mol of 2-(2-furylvinylene)benzothiazole, 15 cm of anhydrous acetone, acetonitrile or tetrahydrofuran and 0.015 mol of methyl iodide were heated for 6 h at 50 to 60 °C. The crystalline fraction was crystallized from methanol. M.p. 256 to 260, yield 31%. For C^H^INOS m.h. 369.20, calculated % C = 46.46, % H = 3.33, % N = 3.88, % S = 8.89. Found % C = 46.09, % H = 3.25, % N = 3.69, % S = 9.09.

Example 3

2-(2-Furylvinylene)-3-allylbenzothiazolium bromide

0.01 mol of 2-(2-furylvinylene)benzothiazole, 20 cc of anhydrous acetonitrile and 0.015 mol of allyl bromide are heated for 8 h at a temperature of 60 to 80 °C. M.p. 198 to 200, yield 21%. For

C.,H..BrNOS m.h. 348.26, calculated % C = 55.00, % H = 4.03, % N = 4.01, % S = 9.18. Found 1 o 14 % C = 54.51, % H = 4.27, % N = 3.78, % S = 8.86.

Example 4

2-(2-Furylvinylene)-3-ethoxycarbonylmethylbenzothiazolium bromide

0.01 mol of 2-(2-furylvinylene)benzothiazole, 20 cm ³ of anhydrous acetonitrile or tetrahydrofuran and 0.015 mol of ethyl bromoacetate were heated for 18 h at 70 to 80 °C. For C ₁₇ H _1g BrNO ₃ S m/z 394.28, calculated i C = 51.52, % H = 4.14, % N = 3.51, % S = 8.11. Found % C = 51.15, % H = 3.98, % N = 3.40, % S = 8.04.

Example 5

2-(2-furylvinylene)-3-benzylbenzothiazolium perchlorate

0.01 mol of 2-(2-furylvinylether)-3-benzylbenzothiazolium bromide is dissolved in 20 cm3 of methanol under heat. 0.02 mol of KCIO^ or NaClO^ in 10 to 15 cm3 of water is gradually added to the solution with stirring. After 5 min. the isolated crystalline product is washed with cold water. M.p. 204 to 210, yield 90%. For ^C 20 ^H 16 ^C3N °5 ^S ' mh 417.87, calculated i C = 57.48, % H = 3.86, i N = 3.35, % S = 7.67. Found i C = 57.31, % H = 3.69, % N = 3.38, % S = 7.72.

Example 6

2-(2-Furylvinylene-3-benzylbenzothiazolium nitrate).

0.01 mol of 2-(2-furylvinylene)-3-benzylbenzothiazolium bromide is dissolved in 20 cm ³ of methanol while hot. 0.02 mol of KNO^ or NaNO^ in 10 ml of water is gradually added to the solution with stirring. After two hours, the isolated crystalline product is washed well with cold water. M.p. 221 to 223, yield 88%. For C ₂ 0 ^H 16 ^N 2°4 ^S mh 380.42 calculated % C = 63.24, % H = 4.24, % N = 7.37, Ϊ S = 8.43. Found % C = 63.37, % H = 4.21, % N = 7.46, % S = 8.22.

Example 7

2-(2-Furylvinylene)-3-benzylbenzothiazolium bromide

About

In 20 cm of anhydrous acetonitrile, 0.01 mol of 2-(2-furylvinylene)benzothiazole and 0.015 mol of benzyl bromide were dissolved. The reaction mixture was heated at 70 to 80 °C for 12 h. The crystalline portion was washed with anhydrous acetone. mp 240 to 242 °C, yield 33%. For C ₂ QH _3g BrNOS, mw 398.31. Calculated % C = 60.30, % .H = 4.05, i N = 3.51, % S = 8.05. Found % e = 59.94, % H = 4.03, % N = 3.53, % S = 9.01.

Example 8

2-(2-furylvinylene)-3-methylbenzothiazolium tetrafluoroborate

0.01 mol of 2-(2-furylvinylene)-3-methylbenzothiazolium iodide is dissolved in 20 cm of methanol

O and gradually with stirring add KBF^ or NaBF^ in 15 cm of water. After one hour the crystalline portion is filtered off and washed with water. M.p. 250 to 251, yield 94%. For C^H-^F^BNOS, m.h. 329.32. Calculated % C = 51.06, % H = 3.67, % N = 4.25, % S = 9.74. Found % C = 50.79, i C = 50.79, % H = 3.76, % N = 4.41, % S = 9.63.

The results of elemental analysis and physicochemical constants of the synthesized compounds according to the invention are shown in Table 1.

Table 1

Characterization of synthesized 2-(2-furylvinylene)-3-substituted benzothiazole salts of formula 1

R-shaped

IH ^{11 CIi} 3 iii ch ₃ !V CH ₃ V CH ₂ CH=CH ₂

VI CH ₂ C ch

VII CH„C,H.

6 5

VIII CH ₂ C _g H ₅ ix ch ₂ c ₆ h ₅ X ch ₂ c ₆ h ₅ XI CH ₂ COOH

XII CH ₂ COOCH ₃

XIII CH ₂ COOC ₂ H ₅ XIV CH ₂ COOC ₃ H _?

XV CH ₂ COOC ₃ H ₇ ~i XVI CH ₂ COOCH-CH ₂

XVII CH ₂ COOCH ₂ CH=CH ₂

XVIII CH-COOCH _n C,H _c 2 2 6 5

I

C10 ₄

BF ₄

Br

Br

Br cio ₄ bf ₄

N0 ₃

Br

Br

Br

Br

Br

Br

Br

Br

Sum. formula M.h. ^{C13H11NO5S2 ​ ​ ​} 325.37 ^C 14 ^H 12 ^OTHER 369.20 c ₁₄ h ₁₂ cino ₅ s 341.77 ^C 14 ^H 12 ^F 4 ^BNOS 329.32 ^{C16H14BrN0S ​ ​} 348.26 ^{C16H12BrNOS ​ ​} 346.19 ^{C20H16BrNOS ​ ​} 398.31 ^{C20H16C1N ° 5S ​} 417.87 ^C 20 ^H 16 ^F 4 ^BNOS 405.42 ^C 20 ^H 16 ^N 2°4 ^S 380.42 ^C 15 ^H 12 ^BrNO 3 ^S 366.23 ^C 16 ^H 14 ^BrNO 3 ^S 380.26 ^c 17H ₁₆ BrN0 ₃ S 394.28 ^C 18 ^H 18 ^BrNO 3 ^S 408.30 ^C 18 ^H 18 ^BrNO 3 ^S 408.30 C _1? H ₁₄ BrNO ₃ S 392.28 ^C 18 ^H 16 ^BrNO 3 ^S 406.31 ^{C22H18BrNO3S ​ ​ ​} 456.35

Calculated/Found T. t. Yield

%C % H % N i with ³ C % 47 98 3 40 3 99 19 70 184-187 42 48 2. / 3 47 4 00 1 9 48 46 46 3 33 3 88 8 89 256-260 31 46 09 3 25 3 69 9 09 49 20 3 54 4 10 9 38 269-271 94 5? 98 06 3 3 39 67 1 41 § tt 250-251 94 50 79 3 76 4 9 63 55 he 4 03 4 01 9 1 8 198-200 21 54 51 4 27 3 /8 8 86 195-197 55 sn 3 49 4 05 9 26 22 55 34 3 48 4 06 8 98 60 30 4 axis 3 51. 8 05 240-242 33 69 84 4 03 3 53 8 01 204-210 57 48 3 86 3 35 7 67 90 57 31 3 69 3 38 7 72 214-216 59 25 3 98 3 45 7 91 71 59 1 8 3 99 .3 50 8 01 221-223 63 24 4 24 7 37 8 43 88 63 37 4 21 7 46 8 22 235-237 49 20 3 30 3 82 8 75 23 48 93 3 16 3 68 8 8.3 193-195 50 21 3 7? 3 68 8 30 38 49 96 3 68 3 58 8 30 194-197 51 5? 4 14 3 51 8 11 40 51 15 3 98 3 40 8 04 185-188 52 96 45 43 7 85 39 52 65 35 42 7 87 156-159 52 96 45 3 43 7 85 40 52 69 45 7.6 7 68 216-219 52 05 3 60 3 57 8 17 40 6? 00 50 60 8 OS 176-179 53 ?1 97 3 45 7 89 28 53 07 74 37 7 96 216-219 57 90 3 97 3 07 7 03 16 57 60 11 88 6 91

IR spectra were measured on a Perkin-Elmer 180 in CHCl3 and corrected for polystyrene. The position of the observed maxima was determined with an accuracy of + 2 cm. IR spectra were measured ~-4 -3 on a Perkin-Elmer 450 spectrophotometer in acetonitrile (o = 10 mol dm ). Extinction coefficients were not determined due to the low light stability of the synthesized compounds. 1H NMR spectra were measured on a TESLA 487 spectrophotometer at 80 MHz in dimethyl sulfoxide with hexamethyldisiloxane as the internal standard. The wavenumber (C=C) was changed with X ^- , resp.

R changes very little except for compounds I and XI. In these two compounds, a significantly lower value of _max in the UV spectra can be observed compared to derivatives II to IV, or XII to XVIII, respectively.

Both derivatives differ from their analogues in that, unlike them, they have the ability to provide specific intra- or intermolecular interactions through the HSO ₄ anion or the carboxyl group of the cation. These processes largely affect the association of these salts.

The measured values are given in Table 2.

Table 2

Values of ¹ H NMR, UV and IR spectra of the synthesized compounds

Compounds- /ppm/ max /C=O/ /C=C/ nina /mm/ /cm ^-1 / /cm ^-1 /

I 6.20-7.80 (ar,-CH-CH-,9H,m) 348 1 600 II 6.15-7.85 (ar,-CH=CH-,9H,m); 3.93 (N ⁺ -CH ₃ , 3H,S) 405 1 612 III 6.17-7.75 (ar,-CH=CH-,9H,m); 3.90 (N ⁺ -CH ₃ , 3H,S) 405 ' 1 613 IV 6.17-7.75 (ar,-CH=CH-,9H,m); 3.90 (N ⁺ -CH ₃ , 3H,a) 404 1 610 in 6.12-7.85 (ar,-CH=CH-,9H,m); 4.63- •5.94 (N ⁺ -CH ₂ CH=CH ₂ , 5R,m) 411 1 613 VI 6.17-7.85 2.25 (CH, (ar,-CH=CH-,9H,m); 1H,S) 5.15 (n' ^I '-CH ₂ -, 2H,s) 415 1 611

Table 2 continued

Compound /ppm/ max /C=0/ /C=C/ /mm/ /cm ^-1 / /cm ^-1 /

VII 6.12-7.87 (ar, -CH=CH- , 14H,m); 5.58 (N ⁺ -CH ₂ -, 2H,s) 412 1 612 VIII 6.10-7.90 (ar, -CHsCH- , 14H,m); 5.55 (N ⁺ -CH ₂ , 2H,s) 413 1 610 IX 6.15-7.90 (ar, -CH=CH- , 14H,m); 5.58 (N ⁺ -CH ₂ ~, 2H,s) 412 1 612 X 6.20-7.95 (ar, -CH=CH, 14H, rn); 5.67 (N ⁺ -CH ₂ -, 2H,s) 412 1 612 XI 6.70-8.50 (ar, -CH=CH- , 9H,m); 5.87 (N ⁺ -CH ₂ -, 2H,s) 402 1 749 1 601 XII 6.12-7.80 (ar, -CH=CH- , 9H,m); 5.31 (N ⁺ -CH.-, 2H,s); 3.55 (O-CH 3' ³ H,s) 417 1 742 1 612 XIII 6.12-7.78 (ar, -CH=CH- , 9H,m); 5.28 (N ⁺ -CH,-, 2H,s); 4.04 (O-CH ₂ -2H ,k); 0, 90 (-CH ₃ , 3H,t) 416 1 746 1 612 XIV 6.17-7.87 (ar, -CH=CH- , 9H,m); 5.34 (N ⁺ -CH ₂ -, 2H,s); 3.90 (O-CH ₂ -, 2 H,t) ; 1.25 (-CH ₂ -, 2H,sx); 0.85 (-C H ₃ , 3H, t) 416 1 746 1 612 XV 6.20-7.80 (ar, -CH=CH- , 9H,m); 5.29 (N ⁺ -CH ₂ -, 2h,s); 4.85 (O-CH , 1H , sp); 0 .89 (CH ₃ -CH-CH ₃ , 6H,á) 416 1 739 1 612 XVI 6.10-7.90 (ar, -CH=CH- , OCH=, 10H,m); 5.42 (N ⁺ -CH,-, 2H,s); 4.42 ( ⁼ CH ₂ -cis, 1H, dd) ; 4 , 70 (=CH ₂ trans, 1H,dd) 418 1 762 1 611 XVII 6.18-7.75 (art. -CH=CH, 9H,m); 4.6-5.6 (-CH=CH , 3H,m) ; 4.42 5.32 (r+-C H _? -, 2H,s); 4.39 (O- _CH2- , 2H,d) 414 1 748 1 612 XVIII 6.20-7.70 (ar, -CH=CH, 14H,m); 5.30 (N ⁺ -CH,-2H) ,s) ! 4.91 (O-CH 2' H,s) 418 1 749 1 612

The substances according to the invention are effective as plant growth regulators. Growth tests were aimed at the prolongation growth of primary roots of vetch (Vicia sativa, var. Fatima). The tested derivatives, depending on the chemical structure and the concentration used, acted to varying degrees on the prolongation growth activity of vetch roots. Example 9 illustrates the method of testing the compounds according to the invention for stimulatory and inhibitory activity.

Example 9

Seeds of vetch were germinated in Petri dishes in a thermostat in the dark at 25 °C. After 48 h of growth, the seedlings were exposed to molar solutions of 2-(2-furylvinylene)-3-substituted benzothiazolium salts of the general formula A, where R and X ^- mean the same. Testing was carried out in a conc. scale of 10 mol/dm and after 24 h of incubation the increase in root elongation growth was determined. In each determination, the growth effect in the control series was also determined. The width of the experimental control set, as well as the significance between the sets, were determined biometrically.

Beta-indoleacetic acid (IAA), 2,3-dichlorophenoxyacetic acid (2,4-D) and 2-chloroethyltrimethylammoniumvinylene)-3-substituted salts were tested as standards. In comparison with 2-styryl-3-substituted derivatives, the activity significantly shifts into the stimulation range. Of the 18 derivatives, 3 have higher stimulation activities than IAA (compounds I, IX, XII), but also other derivatives (VI, VII,

XIV, XV, XVIII), are comparable to 2,4-D. The inhibitory activity was manifested in all derivatives up to a concentration of 10 mol/dm and is higher (except for compound I) than in CCC. The results of the stimulating and inhibitory effect of the synthesized compounds according to the invention are shown in Table 3.

Table 3

Dissociation constants, copper molar properties and growth-regulatory efficacy of synthesized compounds

Compound R x 0 To Growth effect Stimulation Inhibition - % 10“ ³ mol dm“ +% mole dm ^-3 I H HSO ₄ 36.45 0.034 74 14.94 10" ¹³ 3.42 II CH ₃ I 44.96 0.006 34 4.52 10 ^-7 87.75 III ch ₃ C1O ₄ 42.39 0.003 62 84.99

I

Table 3 continued

Growth effect

Stimulation Inhibition + %mol dm - % 10 mol dm

IV CH ₃ bf ₄ 42.99 0.005 56 6.56 10~ ¹³ -9 80.96 in ch ₂ =ch ₂ Br 35.36 0.004 01 5.42 10 * 83.91 VI ch ₉ c-ch Br 30.45 0.035 95 10.73 10 ^-9 96.71 -1 1 VII ^{CH2C6H5 ​ ​} Br 37.30 0.003 50 7.23 10 82.12 VIII ^{CH2C6H5 ​ ​} C10 ₄ 43.99 0.005 26 70.19 IX ^{CH2C6H5 ​ ​} bf ₄ 41.39 0.005 39 12.20 10 ^-11 43.90 X CH _n C _c H _c 2 6 5 N°3 41.69 0.007 10 4.93 10 ^-11 63.43' XI ch ₂ cooh Br 41.63 0.002 47 16.19 10 ⁷ XII ch ₂ cooch ₃ Br , 35.36 0.010 86 10.26 10 ^-13 49.12 XIII _{CH2COOC2H5 ​ ​} Br 33.38 0.015 61 72.89 XIV _{CH2COOC3H7 ​ ​} Br 34.89 0.009 46 17.39 10 ⁷ 49.18 XV CH ₂ COOC ₃ H _? -1 Br 35 33 0.004 48 16.78 10 ⁷ 92.63 XVI _CH2COOCH = _CH2 Br 35.11 0.008 00 54.53 XVII _{CH2COOCH2CH = CH2} Br 36.76 0.005 24 -11 43.04 XVIII ch ₉ cooch ₉ c _a h,. Br 34.11 0.010 08 9.35 10 71.68 IAA 10.20 10 ¹² 39.69/10 ^-6 2,4-B 8.74 io ^-12 45.53/10 ^-5 ccc 4.38

For the synthesized compounds, molar 2 conductivities (Λ) were measured conductometrically in anhydrous ethanol, and values for the dependence; F ( A on cf )F at 7 concentrations were calculated. From the measured values, the dissociation constants (K) and the average molar conductivities (A) (Table 3) were calculated by the Fouss-Kraus method (Fouss R. Μ., Kraus CH. A., J. Am. Chem. Soc. 55, 476 (1923). Observing the relationship between K and biological activity, it was found that at the highest K or at low molar conductivities we can expect the highest activity: in the field of plant growth regulation. (Compounds I, VI, XII, XIII, XVIII). The values obtained also allow a more detailed analysis of the relationship between ions and biological activity. Compounds II to IV dissociate into the same cation and different anions, which represent changes in K values. Arranging the anions according to increasing K gives the order C1O.<^BF _Á <^I <^HSO .. The highest K is for compound I, which ^{44 4} -13 3 also has the highest stimulating efficacy; at the lowest tested concentration of 10 mol/dm.

It can be assumed that the ionic interaction of the cation and anion is low and the interaction of ions with solvent molecules is higher. The lowest K is for compound III, whose inhibitory activity

-3 -3 in the entire test range was maximally manifested only at a conc. 10 mol/dm . The stimulating efficiency of compounds II and IV and compared to the standards is uninteresting. The explanation of the higher Ka.biological activity of compounds VI compared to V, we again find in the low Λθ/ i.e., that there is an increased interaction with solvent molecules. Next group (compounds VII to X) the anion has the same function as in the "first group. The ranking of anions with increasing K is Br <^C1O^<^BF^, while the difference between compounds VIII and IX is minimal.

Explanations:

I 2-(2-furylvinylene)benzothiazolium hydrosulfate II 2-(2-furylvinylene)-3-methylbenzothiazolium iodide

III 2-(2-furylvinylene)-3-methylbenzothiazolium perchlorate IV 2-(2-furylvinylene)-3-methylbenzothiazolium tetrafluoroborate

V 2-(2-furylvinylene)-3-allylbenzothiazolium bromide VI 2-(2-furylvinylene)-3-propargylbenzothiazolium bromide

VII 2-(2-furylvinylene)-3-benzylbenzothiazolium bromide VIII 2-(2-furylvinylene)-3-benzylbenzothiazolium perchlorate

IX 2-(2-furylvinylene)-3-benzylbenzothiazolium tetrafluoroborate X 2-(2-furylvinylene)-3-benzylbenzothiazolium nitrate

XI 2-(2-furylvinylene)-3-carboxymethylbenzothiazolium bromide XII 2-(2-furylvinylene)-3-methoxycarbonylmethylbenzothiazolium bromide

XIII 2-(2-furylvinylene)-3-ethoxycarbonylmethylbenzothiazolium bromide XIV 2-(2-furylvinylene)-3-propoxycarbonylmethylbenzothiazolium bromide

XV 2-(2-furylvinylene)-3-isopropoxycarbonylmethylbenzothiazolium bromide XVI 2-(2-furylvinylene)-3-vinyloxycarbonylmethylbenzothiazolium bromide

XVII 2-(2-furylvinylene)-3-allyloxycarbonylmethylbenzothiazolium bromide XVIII 2-(2-furylvinylene)-3-benzyloxycarbonylmethylbenzothiazolium bromide

Claims (7)

265759 8 IX 2- (2-furylvinylene) -3-benzylbenzothiazolium tetrafluoroborate X 2- (2-furylvinylene) -3-benzylbenzothiazolium nitrate XI 2- (2-furylvinylene) -3-methoxycarbonylmethylbenzothiazolium bromide XIII 2 - (2-furylvinylene) -3-ethoxycarbonylmethylbenzothiazolium bromideXIV 2- (2-furylvinylene) -3-propoxycarbonylmethylbenzothiazolium bromide XV 2- (2-furylvinylene) -3-vinyloxycarbonylmethylbenzothiazolium bromide 2- (2-furylvinylene) -3-benzyloxycarbonylmethylbenzothiazolium bromide (2- (2-furylvinylene) -3-substituted benzothiazolium salts of formula A) (A) wherein R is hydrogen and X is HSO2 or R is methyl and X is J-, C10-6 or BF3 or R is benzyl and X is Br, C10-6, BF3 or NO4 or R is allyl, propargyl, carboxymethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, vinyloxycarbonylmethyl, allyloxycarbonylmethyl or benzyloxycarbonylmethyl and X denotes Br-. 2. A process for the preparation of 2- (2-furylvinylene) benzothiazolium sulphate according to claim 1, characterized in that the 2- (2-furylvinylene) benzothiazole of formula B (B) is treated with sulfuric acid in anhydrous acetone or tetrahydrofuran. 3. A process for preparing 2- (2-furylvinylene) -3-methylbenzothiazolium iodide according to claim 1, wherein the compound of formula B is treated with methyl iodide in anhydrous acetone, tetrahydrofuran or acetonitrile. 4. A process for the preparation of the compounds of formula (1), wherein R is allyl, propargyl, benzyl, carboxymethyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, isopropoxycarbonylmethyl, vinyloxycarbonylmethyl, allyloxycarbonylmethyl, benzyloxycarbonyl-methyl, and X- is bromine, B is treated with a compound of formula RBr, wherein R is as defined above in acetonitrile or tetrahydrofuran. 9 265759 5. A process for the preparation of the compounds of formula (1), wherein R is methyl and X- is C10-6 or BF3, characterized in that 2- (2-furylvinylene) -3-methylbenzothiazolium iodide is a compound of formula (MeX). wherein Me is sodium or potassium and X1 is C10-6 or BF3 in methanol. 6. A process for the preparation of the compounds of formula (1), wherein R is benzyl and &quot; is ClO &quot; X1 is as defined in point 5, in methanol. 7. A method of preparing 2- (2-furylvinylene (-3-benzothiazolium nitrate) according to claim 1, wherein the 2- (2-furylvinylene (-3-benzylbenzothiazolium bromide) bromide is treated with a compound of general formula MeNOg wherein Me is as defined above in methanol.