Synthesis and characterization of novel dithiocarbamic thioanhydrides and their application for plant growth stimulant and phytotoxic activity | Scientific Reports

Scientific Reports volume 14, Article number: 24778 (2024) Cite this article

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In this study, nineteen thioanhydrides were synthesized from the S-acylation reaction of sodium dithiocarbamates with various acyl chlorides in chloroform at room temperature. The synthesized thioanhydrides were evaluated for their growth-stimulating and phytotoxic activities. Benzoic (1a), 4-methoxy- (1b), 4-chloro- (1c), 2-bromo- (1e), 4-fluoro- (1f.) and 4-nitrobenzoic 1H-1,2,4-triazole-1-carbothioic thioanhydrides (1 g) showed moderate to excellent growth-stimulating activity, along with this (1c) exhibited excellent phytotoxic activity, 2,4-dichlorobenzoic 1H-1,2,4-triazole-1-carbothioic thioanhydride (1d) and 2,4-dichlorobenzoic pyrrolidine-1-carbothioic thioanhydride (2b) demonstrated inhibiting and moderate phytotoxic activities. Thioanhydrides (1a-c, 1f., 1 g) exhibited excellent germination energy and germination capacity of wheat seeds: 1a 82 and 90%, 1c 80 and 84%, 1 g 82 and 90% (0.01 mg/ml); 1b, 1 g 78 and 94%, 1c 78 and 90%, 1f. 80 and 94% (0.1 mg/ml). Thioanhydride (1e) showed moderate activity, germination energy and germination capacity were 72 and 76% (0.1 mg/ml), 78 and 84% (0.01 mg/ml). Thioanhydride (1d) demonstrated activity as a growth inhibitor with germination energy, and germination capacity 54 and 58% (0.1 mg/ml), 44 and 42% (0.01 mg/ml). Thioanhydride (1c) exhibited excellent phytotoxic activity analogically to herbicide 2,4-D only on lettuce seeds. Compounds (1d and 2b) were moderately active, inhibiting the growth of lettuce and bent grass seedlings.

Dithiocarbamates are an important class of sulfur-containing compounds due to their wide applications in synthetic organic chemistry, pharmaceuticals, and agrochemicals1,2. One of the preparative methods for synthesizing of dithiocarbamates is the thiolation of the N–H bond with carbon disulfide in the presence of sodium or potassium hydroxide. However, many interesting synthetically different methods have been developed for the synthesis of different kinds of dithiocarbamates during the past few years3,4. One-pot multicomponent syntheses were reported as highly efficient and green methods for the synthesis of dithiocarbamates derivatives with diverse functional groups6,7,8,9,10. In addition, dithiocarbamates are soft sulfur donor ligands capable of easily forming stable complexes with transition metals.

On the other hand, increased interest in dithiocarbamates is due to various biological activities such as cytotoxic11, antitumor, antiproliferative12,13,14,15, antifungal16,17, antimicrobial18,19, and antioxidant15. Furthermore, metal dithiocarbamates complexes have attracted considerable attention for their biological activities. The nature of the metal, its oxidation state, and the nature of a coordinating dithiocarbamate ligand have been known to affect the biological properties and determine their usefulness. Dithiocarbamate ligands with the following metals have shown activities: with copper (II) and cobalt (III) antimicrobial20,21,22,23; with zinc (II) and tin (IV) cytotoxic, antibacterial, antifungal, antileishmanial24,25,26,27; with silver (I) antimicrobial and antioxidant28; with gold (III) and ruthenium (III) anticancer29,30.

Moreover, dithiocarbamate ligands are used as chelators to remove toxic heavy metals (Pd, Cd) from polluted water31,32, corrosion inhibitors33,34, flotation collectors35,36 and vulcanization accelerators37 in material science. Therefore, the synthesis of dithiocarbamates derivatives has recently received considerable attention.

However, there are few recent references to the use of dithiocarbamates in agriculture. An up-to-date and detailed account of various areas of dithiocarbamates applications including synthesis, medicine, industries, catalysisб and agriculture was given in the review38. According to the presented in the review38 statistics of publications on dithiocarbamates from 2015 to 2021, applications of dithiocarbamates in agriculture were discussed only in 2,7% of all publications. Preparations Zineb, Maneb, Mancozeb, Nabam, Carbaryl, Methiocarb, and others are known, used as fungicides, and insecticide, but there is no data on dithiocarbamate-containing plant growth stimulants. Consequently, the need to study the synthesis of novel dithiocarbamate thioanhydrides based on heterocyclic amines to develop new plant growth stimulants and herbicides for agriculture. We previously reported dithiocarbamates with growth-stimulating activity39. This work is a continuation of our study of dithiocarbamate compounds and their biological activity.

The thioanhydrides were synthesized by the S-acylation reaction of sodium dithiocarbamates with appropriate acyl chlorides in chloroform at room temperature according to the steps shown in Scheme 1. Sodium dithiocarbamates (1–3) were prepared by the reaction of heterocyclic amine (1H-1,2,4-triazole, pyrrolidine, 5-methyl-1H-benzo[d][1,2,3]triazole) with carbon disulfide in the presence of sodium hydroxide.

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To synthesize various thioanhydrides, we examined acid chlorides (benzoyl, 4-methoxybenzoyl, 3,4-dimethoxybenzoyl, 4-chlorobenzoyl, 2,4-dichlorobenzoyl, 2-bromobenzoyl, 4-fluorobenzoyl, 4-nitrobenzoyl, 3,5-dinitrobenzoyl, acetyl, 2-phenoxyacetyl, cyclopropanecarboxyl). The novel synthesized compounds (1a-h, 2a-e, 3a-f) from good to excellent yields are presented in Table 1.

The composition and individuality of synthesized compounds were confirmed by elemental analysis, TLC, and IR spectroscopy. The IR spectra of thioanhydrides (1a-h, 2a-e, 3a-f) show an absorption band at 1008–1096 cm-1, which are assigned to ʋ (C=S) stretching vibrations. Bands at 619–694 cm-1 are attributed to the ʋ (C−S) vibrations. The existence of ʋ (C=O) intense vibration bands at 1600–1739 cm-1 indicates thioanhydrides formation.

The structure of thioanhydrides (1a-h, 2a-e, 3a-f) was established based on 1H and 13C NMR spectrum analysis. Characteristic signals from all protons and carbons in synthesized molecules (1a-h, 2a-e, 3a-f) are presented in the experimental section “Experimental”. In the 1H and 13C NMR spectrum values of chemical shifts data for heterocyclic thioanhydrides (1a-h, 2a-e, 3a-f) with integration and multiplicity pattern as expected, confirm their formation. Singlet signals for two protons of triazole moiety appeared at 8.19–8.32 and 9.34–9.41 ppm in the 1H NMR of compounds (1a-h). A multiplet signal for methylene protons at 1.71–1.79 ppm and two triplet signals for another methylene protons at 3.02–3.32 and 3.40–3.45 ppm of pyrrolidine moiety occurred in the 1H NMR of compounds (2a-e). Chemical shifts for the aromatic protons for all thioanhidrides (1a-h, 2a-e, 3a-f) are found in the appropriate low field region at 6–8 ppm.

In the 13C NMR spectra, the carbon atoms of the C=O and C=S groups resonated in the downfield region at 163.3 – 176.2 ppm, which confirm the formation of thioanhydrides. All theoretical predicted chemical shift values of protons and carbon atoms are in good coherence with the experimental values 1H and 13C NMR spectra.

The synthesized thioanhydrides (1a-g) were screened for their growth-stimulating activity on wheat seeds. The effect of the test compounds on germination energy and capacity and on morphometric indicators (i.e., length of shoots and roots, number of roots, weight of shoots and roots) of spring wheat sprouts was studied. The growth-stimulating screening results are summarized in Fig. 1. Among the tested preparations, compounds (1a-c, 1f., 1 g) exhibited excellent growth-stimulating activity at both concentrations 0.1 and 0.01 mg/ml compared to the control (water) and reference standards (KN-2, AN-16) at same concentrations. This is evidenced by the received results of germination energy and germination capacity of wheat seeds treated with test compounds (1a-c, 1f., 1 g) (Fig. 1a, c, e, i). Therefore, the following compounds showed a high germination energy and germination capacity: 1a 82 and 90%, 1c 80 and 84%, 1 g 82 and 90%, 1f. 76 and 90% at 0.01 mg/ml concentration; 1b, 1 g 78 and 94%, 1c 78 and 90%, 1f. 80 and 94% at 0.1 mg/ml concentration. Whereas the control (water) and reference standards (KN-2, AN-16) showed at appropriate concentrations low values of germination energy from 46 to 76% and germination capacity from 56 to 84% (Fig. 1a, c, e, i). Germination energy by 6 – 36% and germination capacity by 2 – 34% were increased compared to the control and reference standards (KN-2, AN-16). It should be noted that compounds 1c and 1f. improve germination energy by 20 – 34%.

Germination energy and germination capacity, and morphometric indicators of wheat seeds by treating thioanhydrides (1a-g) compared to the control (water) and reference standards (KN-2, AN-16): a and b compound (1a), c and d – (1c), e and f – (1b, 1d, 1 g), g and h – (1e), i and j – (1f.).

Furthermore, the treatment with thioanhydrides (1a and 1 g), except the compounds (1b 1c, and 1f.), has a positive effect on the morphometric indicators of wheat seeds. These compounds (1a and 1 g) increased the number of roots, shoots, root lengths, and the weight of fresh roots and green shoots. As shown in Fig. 1b, compound (1a) at a concentration of 0.01 mg/ml exhibited excellent growth stimulating activity, where shoot and root lengths were 8.60 and 6.85 cm, the number of roots was 4.93 pcs, the weight of fresh roots and of green shoots were 1.24 and 1.45 g.

Noticeably, the compound (1 g) showed good activity compared only to the control (water) and standard (KN-2) and at concentration 0.1 mg/ml. For compound (1 g), the following values of morphometric indicators were obtained: shoot and root lengths were 8.52 and 7.66 cm, the number of roots was 4.91 pcs, and the weight of fresh roots and of green shoots were 1.14 and 1.11 g (Fig. 1f).

Despite the fact, that compounds (1b, 1c, and 1f.) increased germination energy and germination capacity of wheat seeds, the morphometric indicators of seeds were at the same level as the control (water) and reference standards (KN-2, AN-16), differing slightly.

Thioanhydride (1e) showed lower activity than reference standards (KN-2, AN-16). As shown in Fig. 1g, germination energy and germination capacity were 72 and 76% (0.1 mg/ml), 78 and 84% (0.01 mg/ml), but were higher than control (water) (44 and 46%), accordingly. The morphometric indicators of seeds were slightly worse than reference standards (KN-2, AN-16) and better than the control (Fig. 1h).

In addition, test results showed that compound (1d) exhibits as a growth inhibitor. Thus, germination energy and germination capacity were 54 and 58% (0.1 mg/ml), 44 and 42% (0.01 mg/ml), whereas the control (water) (56 and 84%) and reference standards KN-2 (62 and 68–70%), AN-16 (72–76 and 80–82%) showed good activity (Fig. 1e). In addition, the morphometric indicators were lower compared to the control (water) and reference standards (KN-2, AN-16), too (Fig. 1f). In this case, compound (1d) inhibits germination of wheat seeds.

The synthesized thioanhydrides (1c, 1d, 2b) were screened for phytotoxic activity on lettuce (Lactuca sativa) and bent grass (Agrostis stolonifera) seeds. The phytotoxic activity bioassay results are presented in Fig. 2. Among the tested compounds, thioanhydride (1c) exhibited excellent phytotoxic activity on lettuce at all concentrations (0,01; 0,03; 0,1; 0,3; 0,5; 1 mg/ml) similarly to herbicide 2,4-D. The phytotoxicity was assessed on the scale as of 5 points in all cases. However, compound (1c) showed no activity on bent grass seeds.

The bioassay for phytotoxic activity: a Herbicide 2,4 D, b compound (1c), c compound (1d), d compound (2b) on lettuce (Lactuca sativa); e Herbicide 2,4 D, f compound (1c), g compound (1d), h compound (2b) on bentgrass (Agrostis stolonifera) seeds.

Compound (1d) was moderately active on lettuce seeds at all concentrations and in this case phytotoxicity was assessed on scale as 4 (0.01 mg/ml) and 3 (0,03; 0,1; 0,3; 0,5; 1 mg/ml) points compared to herbicide 2,4-D, which was rated at 4 (0,01; 0,03; 0,1 mg/ml) and 5 (0,3; 0,5; 1 mg/ml) points. With that thioanhydride (1d) showed low phytotoxic activity on bent grass. The phytotoxicity was assessed on the scale as of 2 points (0,01; 0,03; 0,1 mg/ml) and was not effect at other concentrations (0,3; 0,5; 1 mg/ml).

Compound (2b) was moderately active compared to herbicide 2,4-D on both species at 1 mg/mL and inhibited the growth of the seedlings at this concentration. The phytotoxicity was assessed on the scale as of 3 points on lettuce and bent grass. The herbicide 2,4-D was rated at 5 points. No effect was observed at other concentrations (0.1; 0.02; 0.2; 2; 0.03; 0.3; 3 mg/ml).

The structure–activity relationship among 1H-1,2,4-triazole-1-carbothioic thioanhydrides (1a-g) revealed that the presence of unsubstituted phenyl group and methoxy, chlorine, fluorine at the phenyl group showed good to excellent growth-stimulating activity. In contrast, the bromine in the phenyl group showed moderate activity. It was noticed that the presence second chlorine atom at the phenyl group of both 1H-1,2,4-triazole and pyrrolidine-based thioanhydrides showed inhibited and phytotoxic activities.

In conclusion, we have synthesized a series of novel nineteen thioanhydrides based on heterocyclic dithiocarbamates. The desired products were finished exhibiting good to excellent yields (58–94%) by the S-acylation reaction of sodium dithiocarbamates with appropriate acyl chlorides in chloroform. The biological studies revealed that dithiocarbamic thioanhydrides exhibited moderate to excellent growth-stimulating and phytotoxic activities. It was established that thioanhydrides (1a-1c, 1f., 1 g) increase germination energy and germination capacity of wheat seeds: 1a 82 and 90%, 1c 80 and 84%, 1 g 82 and 90%, 1f. 76 and 90% at 0.01 mg/ml concentration; 1b, 1 g 78 and 94%, 1c 78 and 90%, 1f. 80 and 94%at 0.1 mg/ml concentration. Whereas, the control (water) and reference standards (KN-2, AN-16) have at appropriate concentrations low values of germination energy from 46 to 76% and germination capacity from 56 to 84%. Germination energy by 6 – 36% and germination capacity by 2 – 34% were increased compared to the control and reference standards (KN-2, AN-16). Wherein compounds 1c and 1f. improve germination energy by 20 – 34%.

Moreover, thioanhydrides (1a and 1 g) have a excellent effect on the morphometric indicators of wheat seeds, increasing the number of roots, shoots and root lengths, and the weight of fresh roots and green shoots.

Thioanhydride (1e) showed moderate activity, germination energy and germination capacity were 72 and 76% (0.1 mg/ml), 78 and 84% (0.01 mg/ml). Its growth-stimulating activity is lower than reference standards (KN-2, AN-16), but is higher than control (44 and 46%).

Compound (1d) inhibited wheat-seed germination energy and capacity as the growth inhibitor. Thioanhydride (1d) inhibits germination energy (54 and 58%, 0.1 mg/ml) and germination capacity (44 and 42%, 0.01 mg/ml).

The phytotoxic bioassay results showed that thioanhydride (1c) exhibited excellent activity at all tested concentrations (0,01; 0,03; 0,1; 0,3; 0,5; 1 mg/ml), inhibiting the growth of lettuce seeds (Lactuca sativa) analogically to herbicide 2,4-D. Thioanhydrides (1d and 2b) were moderately active compared to herbicide 2,4-D, inhibiting the growth of the seedlings.

Thus, dithiocarbamic thioanhydrides would be considered promising candidates for further optimization to develop new plant growth stimulants and herbicides.

All starting reagents with a stated purity were purchased from Sigma-Aldrich and used without further purification: 5-methyl-1H-benzo[d][1,2,3]triazole-1-carbodithioate, 98%; 1H-1,2,4-triazole-1-carbodithioate, 98%; pyrrolidine, 99%; carbon disulfide, 99.9%; acyl chlorides with a stated purity of 98–99%. The reaction progress and purity of the synthesized products were controlled using TLC on silica gel 60 (0.20 mm) plates with fluorescent indicator UV-254. The eluents for TLC analysis were acetone-hexane (1:3). The melting point was determined on a Hanon MP450 apparatus (China). Elemental analysis was carried out on a Rapid Micro N Cube elemental analyzer (Germany), Cl with IR detection optional. The IR spectra were recorded on a Thermo Scientific Nicolet 5700 FTIR spectrometer (USA) as KBr pellets. The 1H (400 MHz) and 13C (100 MHz) NMR spectra were recorded on a JNM-ECA 400 (Jeol) NMR spectrometer (Japan). Dimethylsulfoxide (DMSO-d6) was used as the solvent and tetramethyl silane (TMS) as the internal standard. A gas chromatograph with mass spectrometric detector Agilent 6890N/5973N was used to record MS spectra.

Sodium 5-methyl-1H-benzo[d][1,2,3]triazole-1-carbodithioate (3). A solution of 5.7 g (0.075 mol) of CS2 in 5 mL of ethanol was added dropwise with stirring to a solution of 3 g (0.075 mol) sodium hydroxide dissolved in 3 mL of water and 10 g (0.075 mol) 5-methyl-1H-benzo[d][1,2,3]triazole in 20 mL of ethanol. The reaction after the addition of carbon disulfide was stirred for 2 h at room temperature. The solvent was removed under reduced pressure, and then to remove the remaining water, the residue was washed with acetonitrile, which was evaporated under reduced pressure. The solid obtained after distillation was washed with hexane and dried. Yield 13.4 g (77%); mp. 88 °C; Rf = 0.71 (H2O).

Sodium 1H-1,2,4-triazole-1-carbodithioate (1). Yield 90%; mp. 78 °C; Rf = 0.83 (H2O).

Sodium pyrrolidine-1-carbodithioate (2). Yield 95%; mp. > 300 °C; Rf = 0.90 (EtOH:H2O, 1:3).

The mixture of the corresponding sodium dithiocarbamate (0.01 mol) and acyl chlorides (0.01 mol) in 25 mL of chloroform was stirred for 2 h at room temperature. The solvent was evaporated under reduced pressure. In the case of crystalline residues, the products were purified by recrystallization from hexane to obtain the desired compounds. For oily compounds (1 h, 2b, 3a, 3f.), the products were purified by washing with the corresponding solvent (hexane, diethyl ether).

Benzoic 1H-1,2,4-triazole-1-carbothioic thioanhydride (1a). Yield 82%; mp. 52 °C; Rf = 0.37 (acetone − hexane, 1:3); IR (KBr, ʋ, cm-1): 1687 (C=O), 1063 (C=S), 675 (C–S); 1H NMR (DMSO-d6, δ, ppm.): 7.51 (t, J = 8.0 Hz, 2H, Ar); 7,66 (t, J = 8.0 Hz, 1H,Ar); 8,02 (d, J = 8.0 Hz, 2H, Ar); 8.30 (s, 1H, N−C(3)H = N Htrz); 9.34 (s, 1H, N − C(5)H = N Htrz); 13C NMR (DMSO-d6, δ, ppm.): 128.9, 130.6, 131.8, 134.6 (Ar); 147.2 (N − C(3)H = N Htrz); 153.9 (N − C(5)H = N) Htrz 165.1 (C=O); 167.9 (C=S); Anal. Calcd for C10H7N3OS2: C, 48.18; H, 2.83; N, 16.85, S, 25.72; Found: C, 48.39; H, 2.97; N, 16.64; S, 25.57; m/z: calculated for C10H7N3OS2: 279.01, found 281.1.

4-Methoxybenzoic 1H-1,2,4-triazole-1-carbothioic thioanhydride (1b). Yield 91%; mp. 81.2 °C; Rf = 0.31 (acetone–hexane, 1:3); IR (KBr, ʋ, cm-1): 1694 (C = O), 1016 (C=S), 619 (C − S); 1H NMR (DMSO-d6, δ, ppm.): 3.82 (s, 3H, OCH3); 7.03 (d, J = 8.0 Hz, 2H, Ar); 8.09 (d, 2H, J = 4.0, 8.0 Hz, Ar); 8.30 (s, 1H, N − C(3)H = N Htrz); 9.31 (s, 1H, N − C(5)H = N Htrz); 13C NMR (DMSO-d6, δ, ppm.): 56.2 (OCH3); 114.5, 122.2, 134.6, 164.6 (Ar); 147.2 (N − C(3)H = N Htrz); 153.7 (N − C(5)H = N Htrz); 163.9 (C=O); 164.6 (C = S); Anal. Calcd for C11H9N3O2S2: C, 47.30; H, 3.25; N, 15.04; S, 22.96; Found: C, 47.57; H, 3.12; N, 14.89; S, 22.75.

4-Chlorobenzoic 1H-1,2,4-triazole-1-carbothioic thioanhydride (1c). Yield 83%; mp. 69.9 °C; Rf = 0.39 (acetone–hexane, 1:3); IR (KBr, ʋ, cm-1): 1715 (C=O), 1094 (C = S), 627 (C–S); 1H NMR (DMSO-d6, δ, ppm.): 7.61 (d, J = 8, 2H, Ar); 8.06 (d, J = 8.0, 2H, Ar); 8.32 (s, 1H, N − C(3)H = N Htrz); 9.38 (s, 1H, N − C(5)H = N Htrz); 13C NMR (DMSO-d6, δ, ppm.): 129.2, 130.2, 131.6, 133.7, 138.3, 139.7 (Ar); 147.4 (N − C(3)H = N Htrz); 154.0 (N − C(5)H = N Htrz) 164.1 (C = O); 167.0 (C = S); Anal. Calcd for C10H6ClN3OS2. C, 42.33; H, 2.13; Cl, 12.49; N, 14.81; S, 22.60; Found: C, 42.44; H, 2.38; Cl, 12.58; N, 14.99; S, 22.82.

2,4-Dichlorobenzoic 1H-1,2,4-triazole-1-carbothioic thioanhydride (1d). Yield 81%; mp. 91 °C, Rf = 0.42 (acetone–hexane, 1:3); IR (KBr, ʋ, cm-1): 1739 (C=O), 1064 (C=S), 667 (C–S); 1H NMR (DMSO-d6, δ, ppm.): 7.55 (dd, J = 8.0 Hz, 1H, Ar); 7.75 (t, J = 8.0 Hz, 2H, Ar); 8.26 (s, 1H, N − C(3)H = N Htrz); 9.41 (s, 1H, N − C(5)H = N Htrz); 13C NMR (DMSO-d6, δ, ppm.): 127.9, 130.1, 130.9, 132.3, 132.6, 137.9 (Ar); 146.7 (N − C(3)H = N Htrz); 154.4 (N − C(5)H = N Htrz); 163.3 (C = O); 166.4 (C=S); Anal. Calcd for C10H5Cl2N3OS2: C, 37.75; H, 1.58; Cl, 22.28; N, 13.21; S, 20.15; Found: C, 37.90; H, 1.76; Cl, 22.39; N, 13.36; S, 20.27.

2-Bromobenzoic 1H-1,2,4-triazole-1-carbothioic thioanhydride (1e). Yield 83%; mp. 118.6 °C; Rf = 0.44 (acetone–hexane, 1:3); IR (KBr, ʋ, cm-1): 1715 (C=O), 1095 (C=S), 626 (C–S); 1H NMR (DMSO-d6, δ, ppm.): 7.57 (t, J = 8.0 Hz, 2H, Ar); 8.04 (t, J = 8.0 Hz, 2H, Ar); 8.31 (s, 1H, N − C(3)H = N Htrz); 9.36 (s, 1H, N − C(5)H = N Htrz); 13C NMR (DMSO-d6, δ, ppm.): 129.1, 133.7, 139.7 (Ar); 147.3 (N − C(3)H = N Htrz); 153.9 (N − C(5)H = N Htrz); 163.9 (C = O), 164.09 (C = S); Anal. Calcd for C10H6BrN3OS2: C, 36.59; H, 1.84; Br, 24.35; N, 12.80; S, 19.54; Found: C, 36.36; H, 1.68; N, 12.99; S, 19.69.

4-Fluorobenzoic 1H-1,2,4-triazole-1-carbothioic thioanhydride (1f.). Yield 62%; mp. 76.9 °C; Rf = 0.41 (acetone–hexane, 1:3); IR (KBr, ʋ, cm-1): 1720 (C=O), 1009 (C = S), 631 (C–S); 1H NMR (DMSO-d6, δ, ppm.): 7.34 (t, J = 8.0 Hz, 2H, Ar), 8.14 (dd, J = 8.0 Hz, 2H, Ar); 8.30 (s, 1H, N − C(3)H = N Htrz); 9.34 (s, 1H, N − C(5)H = N Htrz); 13C NMR (DMSO-d6, δ, ppm.): 116.1, 116.3, 127.1, 135.1, 163.8 (Ar); 147.3 (N − C(3)H = N Htrz); 153.9 (N − C(5)H = N Htrz); 164.7 (C=O); 167.2 (C=S); Anal. Calcd for C10H6FN3OS2: C, 44.93; H, 2.26; F, 7.11; N, 15.72; S, 23.99; Found: C, 44.76; H, 2.09; N, 15.55; S, 24.17.

4-Nitrobenzoic 1H-1,2,4-triazole-1-carbothioic thioanhydride (1 g). Yield 60%; mp. 120.2 °C; Rf = 0.31 (acetone–hexane, 1:3); IR (KBr, ʋ, cm-1): 1709 (C=O), 1058 (C=S), 642 (C–S); 1H NMR (DMSO-d6, δ, ppm.): 8.23 (d, J = 8.0 Hz, 2H, Ar), 8.33 (d, J = 8.0 Hz, 2H, Ar); 8.32 (s, 1H, N − C(3)H = N Htrz); 9.41 (s, 1H, N − C(5)H = N Htrz); 13C NMR (DMSO-d6, δ, ppm.): 123.8, 131.2, 133.0, 136.5, 150.6 (Ar); 147.3 (N − C(3)H = N Htrz); 154.2 (N − C(5)H = N Htrz); 163.9 (C=O); 166.3 (C=S); Anal. Calcd for C10H6N4O3S2: C, 40.81; H, 2.05; N, 19.04; S, 21.79; Found: C, 40.65; H, 1.83; N, 19.21; S, 21.58.

Cyclopropanecarboxylic 1H-1,2,4-triazole-1-carbothioic thioanhydride (1 h). Yield 61%; oil; Rf = 0.39 (acetone–hexane, 1:3); IR (KBr, ʋ, cm-1): 1699 (C = O), 1064 (C = S), 636 (C–S); 1H NMR (DMSO-d6, δ, ppm.): 1.10 (m, 2H, CH2); 1.10 (m, 2H, CH2), 1.16 (m, 2H, CH2); 2.82 (m, 1H, CH); 8.19 (s, 1H, N − C(3)H = N Htrz); 9.14 (s, 1H, N − C(5)H = N Htrz); 13C NMR (DMSO-d6, δ, ppm.): 12.3 (CH2); 13,1 (CH); 144.5 (N − C(3)H = N Htrz); 153.7 (N − C(5)H = N Htrz); 171.9 (C = O); 176.2 (C=S); Anal. Calcd for C7H7N3OS2: C, 39.42; H, 3.31; N, 19.70; S, 30.07; Found: C, 39.25; H, 3.52; N, 19.57; S, 29.79.

4-Chlorobenzoic pyrrolidine-1-carbothioic thioanhydride (2a). Yield 78%; mp. 62 °C; Rf = 0.38 (acetone–hexane, 1:3); IR (KBr, ʋ, cm-1): 1681 (C=O), 1010 (C = S), 694 (C–S); 1H NMR (DMSO-d6, δ, ppm.): 1.77 (m, 4H, C(3,4)H2 Prl); 3.30 (t, J = 4.0, 6.0 Hz, 2H, C(5)H2 Prl); 3.40 (t, J = 4.0, 6.0 Hz, 2H, C(2)H2 Prl); 7.43 (d, J = 8.0 Hz, 2H, Ar); 7.49 (d, J = 8.0 Hz, 2H, Ar); 13C NMR (DMSO-d6, δ, ppm.): 24.4, 26.5 (C(3,4)H2 Prl); 46.5, 49.4 (C(2,5)H2 Prl); 128.8, 129,6, 131.6, 134.9, 136.4 (Ar); 166.9 (C=O); 167.6 (C=S); Anal. Calcd for C12H12ClNOS2: C, 50.39; H, 4.18; Cl, 12.35; N, 4.87; S, 22.45; Found: C, 50.53; H, 4.33; Cl, 12.51; N, 5.05; S, 22.23; m/z: calculated for C12H12ClNOS2: 285.00, found 283.3.

2,4-Dichlorobenzoic pyrrolidine-1-carbothioic thioanhydride (2b). Yield 72%; oil; Rf = 0.60 (acetone–hexane, 1:3); IR (KBr, ʋ, cm-1): 1698 (C=O), 1008 (C=S), 615 (C–S); 1H NMR (DMSO-d6, δ, ppm.): 1.77 (m, 4H, C(3,4)H2 Prl); 3.02 (t, J = 4.0, 6.0 Hz, 2H, C(5)H2 Pyr); 3.41 (t, J = 4.0, 6.0 Hz, 2H, C(2)H2 Prl); 7.37 (d, J = 8.0 Hz, 1H, Ar); 7.44 (dt, J = 4.0, 8.0 Hz, 1H, Ar); 7.64 (d, J = 4.0 Hz, 1H Ar); 13C NMR (DMSO-d6, δ, ppm.): 24.5, 25.9 (C(3,4)H2 Prl); 45.8, 47.9 (C(2,5)H2 Prl); 128.4, 129.6, 130.6, 132.8, 134.6, 136.7 (Ar); 164.9 (C=O); 166.5 (C=S); Anal. Calcd for C12H11Cl2NOS2: C, 44.98; H, 3.41; Cl, 22.18; N, 4.32; S, 19.96; Found: C, 45.15; H, 3.26; Cl, 22.02; N, 4.57; S, 20.22.

4-Fluorobenzoic pyrrolidine-1-carbothioic thioanhydride (2c). Yield 61%; mp. 60 °C; Rf = 0.31 (acetone–hexane, 1:3); IR (KBr, ʋ, cm-1): 1601 (C=O), 1096 (C=S), 682 (C–S); 1H NMR (DMSO-d6, δ, ppm.): 1.78 (m, 4H, C(3,4)H2 Prl); 3.32 (t, J = 8.0 Hz, 2H, C(5)H2 Prl); 3.40 (t, J = 8.0 Hz, 2H, C(2)H2 Prl); 7.19 (t, J = 8.0, 2H, Ar); 7.54 (t, J = 8.0 Hz, 2H, Ar); 13C NMR (DMSO-d6, δ, ppm.): 24.4, 26.5 (C(3,4)H2 Prl); 46.5, 49.5 (C(2,5)H2 Prl); 115.6 (d, J13C-19F = 22), 130.1, 134.1, 161.6 (Ar); 164.4 (C(Ar) − F); 167.8 (C=O), (C=S); Anal. Calcd for C12H12FNOS2: C, 53.48; H, 4.45; F, 6.98; N, 5.21; S, 23.76; Found: C, 53.65; H, 4.59; N, 5.40; S, 23.91.

3,5-Dinitrobenzoic pyrrolidine-1-carbothioic thioanhydride (2d). Yield 83%; mp. 156 °C; Rf = 0.21 (acetone–hexane, 1:3); IR (KBr, ʋ, cm-1): 1620 (C=O), 1076 (C=S), 694 (C–S); 1H NMR (DMSO-d6, δ, ppm.): 1.79 (m, 4H, C(3,4)H2 Prl); 3.37 (t, J = 4.0 Hz, 2H, C(5)H2 Prl); 3.45 (t, J = 4.0 Hz, 2H, C(2)H2 Prl); 8.62 (s, 1H, Ar); 8.80 (s,1H, Ar), 9.35 (s, 1H, Ar); 13C NMR (DMSO-d6, δ, ppm.): 24.3, 26.4 (C(3,4)H2 Prl); 44.9, 49.3 (C(2,5)H2 Prl); 119.8, 127.9, 140.5, 148.5 (Ar); 164.4 (C=O); Anal. Calcd for C12H11N3O5S2: C, 42.22; H, 3.25; N, 12.31; S, 18.78; Found: C, 42.37; H, 3.02; N, 12.01; S, 18.47; m/z: calculated for C12H11N3O5S2: 341.01, found 341.3.

2-Phenoxyacetic pyrrolidine-1-carbothioic thioanhydride (2e). Yield 64%; mp. 65 °C; Rf = 0.30 (acetone–hexane, 1:3); IR (KBr, ʋ, cm-1): 1647 (C=O), 1076 (C=S), 690 (C–S); 1H NMR (DMSO-d6, δ, ppm.): 1.71 (m, 2H, C(3)H2 Prl); 1.83 (m, 2H, C(4)H2 Prl); 3.27 (t, J = 4.0, 6.0 Hz, 2H, C(2)H2 Prl); 3.41 (t, J = 4.0, 6.0 Hz, 2H, C(5)H2 Pyr); 4.66 (s, 2H, OCH2); 6.88 (d, J = 8.0 Hz, 2H, Ar); 6.89 (t, J = 8.0 Hz, 1H, Ar); 7.23 (t, J = 8.0 Hz, 2H, Ar); 13C NMR (DMSO-d6, δ, ppm.): 24.0, 26.2 (C(3,4)H2 Prl); 45.3, 46.1 (C(2,5)H2 Prl); 66.8 (OCH2), 115.1, 121.3, 129.9, 158.7 (Ar); 166.3 (C=O); Anal. Calcd for C13H15NO2S2: C, 55.45; H, 5.39; N, 4.92; S, 22.81; Found: C, 55.37; H, 5.17; N, 4.68; S, 22.59; m/z: calculated for C13H15NO2S2: 281.05, found 281.1.

Acetic 5-methyl-1H-benzo[d][1,2,3]triazole-1-carbothioic thioanhydride (3a). Yield 94%; oil; Rf = 0.32 (acetone − hexane, 1:3); IR (KBr, ʋ, cm-1): 1705 (C=O), 1076 (C=S), 667 (C–S); 1H NMR (DMSO-d6, δ, ppm.): 2.25 (s, 6H, 2CH3); 7.01 (d, J = 8.0 Hz, 1H, Ar); 7.47 (s, 1H, Ar); 7,66 (d, J = 8.0 Hz, 1H, Ar); 13C NMR (DMSO-d6, δ, ppm.): 21.4 (CH3); 113.2, 115.6, 127.5, 135.8, 138.6, 139.1 (Ar); 169.8 (C=O); 172.7 (C=S); Anal. Calcd for C10H9N3OS2: C, 47.79; H, 3.61; N, 16.72; S, 25.52; Found: C, 47.58; H, 3.37; N, 16.91; S, 25.76; m/z: calculated for C10H9N3OS2: 251.02, found 249.9.

4-Methoxybenzoic 5-methyl-1H-benzo[d][1,2,3]triazole-1-carbothioic thioanhydride (3b). Yield 78%; mp. 95 °C; Rf = 0.45 (acetone − hexane, 1:3); IR (KBr, ʋ, cm-1): 1697 (C = O), 1047 (C = S), 641 (C–S); 1H NMR (DMSO-d6, δ, ppm.): 2.38 (s, 3H, CH3); 3.83 (d, J = 3.5 Hz, 3H, OCH3); 7.08 (d, J = 8.4 Hz, 1H, Ar); 7,72 (d, J = 8.4 Hz, 1H, Ar); 7.94 (s, 1H, Ar); 8.01 (d, J = 8.4 Hz, 1H, Ar); 8.08 (d, J = 8.4 Hz, 1H, Ar); 13C NMR (DMSO-d6, δ, ppm.): 21.8 (CH3), 55.9 (OCH3); 114.3, 115.8, 119.8, 123.7, 132.8, 134.6, 135.8, 136.7, 141.5, 144.2, 146.1 (Ar); 164.3 (C = O); 165.8 (C = S); Anal. Calcd for C16H13N3O2S2: C, 55.96; H, 3.82; N, 12.24; S, 18.67; Found: C, 56.17; H, 3.63; N, 12.01; S, 18.49; m/z: calculated for C16H13N3O2S2: 343.04, found 340.9.

3,4-Dimethoxybenzoic 5-methyl-1H-benzo[d][1,2,3]triazole-1-carbothioic thioanhydride (3c). Yield 74%; mp. 82 °C; Rf = 0.18 (acetone-hexane, 1:3); IR (KBr, ʋ, cm-1): 1677 (C=O), 1019 (C=S), 626 (C–S); 1H NMR (DMSO-d6, δ, ppm.): 2.36 (s, 3H, CH3); 3.71 (s, 6H, 2OCH3); 6.80 (d, J = 8.0 Hz, 1H, Ar); 6.96 (d, J = 8.0 Hz, 1H, Ar); 7.56 (d, 3H, Ar); 7,67 (d, J = 8.0 Hz, 1H, Ar); 13C NMR (DMSO-d6, δ, ppm.): 21.8 (CH3); 55.9 (OCH3); 110.8, 113.4, 114.6, 115.9, 122.8, 124.9, 132.3, 132.5, 141.8, 142.5, 148.1, 150.5 (Ar); 171.6 (C=O, C=S); Anal. Calcd for C17H15N3O3S2: C, 54.67; H, 4.05; N, 11.25; S, 17.17; Found: C, 54.51; H, 4.17; N, 11.06; S, 17.05.

2-Bromobenzoic 5-methyl-1H-benzo[d][1,2,3]triazole-1-carbothioic thioanhydride (3d). Yield 84%; mp. 103.8 °C; Rf = 0.50 (acetone-hexane, 1:3); IR (KBr, ʋ, cm-1): 1706 (C = O), 1053 (C=S), 623 (C–S); 1H NMR (DMSO-d6, δ, ppm.): 2.45 (s, 3H, CH3); 7.38 (d, J = 8.0 Hz, 1H, Ar); 7.54 (d, J = 8.0 Hz, 1H, Ar); 7.63 (d, J = 8.0 Hz, 1H, Ar); 7.93 (s, 1H, Ar); 8.05 (t, J = 8.0 Hz, 2H, Ar); 8.06 (d, J = 8.0 Hz, 1H, Ar); 13C NMR (DMSO-d6, δ, ppm.): 21.3 (CH3); 114.3, 119.5, 129.1, 130.8, 132.6, 133.7, 137.1, 139.1, 141.9, 144.3, 146.2 (Ar); 165.8 (C=O), 165.9 (C=S); Anal. Calcd for C15H10BrN3OS2: C, 45.92; H, 2.57; Br, 20.37; N, 10.71; S, 16.35; Found: C, 45.77; H, 2.40; N, 10.59; S, 16.26.

3,5-Dinitrobenzoic 5-methyl-1H-benzo[d][1,2,3]triazole-1-carbothioic thioanhydride (3e). Yield 58%; mp. 177.3 °C; Rf = 0.22 (acetone-hexane, 1:3); IR (KBr, ʋ, cm-1): 1714 (C=O), 1054 (C=S), 620 (C–S); 1H NMR (DMSO-d6, δ, ppm.): 2.36 (s, 3H, CH3); 7.48 (s, 1H, Ar); 7.65 (s, 1H, Ar); 8.04 (s, 1H, Ar); 8.78—9.13 (3H, Ar); 13C NMR (DMSO-d6, δ, ppm.): 21.6 (CH3); 114.2, 120.5, 122.7, 122.6, 129.3, 131.5, 132.3, 133.3, 135.3, 137.7, 142.6, 144.4, 148.2, 148.7 (Ar); 164.4 (C=O);Anal. Calcd for C15H9N5O5S2: C, 44.66; H, 2.25; N, 17.36; S, 15.90; Found: C, 44.48; H, 2.13; N, 17.51; S, 15.78.

Cyclopropanecarboxylic 5-methyl-1H-benzo[d][1,2,3]triazole-1-carbothioic thioanhydride (3f.). Yield 86%; oil; Rf = 0.54 (acetone-hexane, 1:3); IR (KBr, ʋ, cm-1): 1713 (C = O), 1049 (C = S), 622 (C–S); 1H NMR (DMSO-d6, δ, ppm.): 1.21 (t, 4H, 2CH2); 2.36 (s, 3H, CH3); 3.14 (m, 1H, CH); 7.55 (s, 1H, Ar); 7.72 (dd, J = 4.3, 8.4 Hz, 1H, Ar); 7.87 (d, J = 8.4 Hz, 1H, Ar); 13C NMR (DMSO-d6, δ, ppm.): 11.9(2CH2), 13.8 (CH), 21.3 (CH3); 113.8, 119.3, 129.2, 136.5, 141.6, 146.5 (Ar); 173.1 (C=O), 173.2 (C=S); Anal. Calcd for C12H11N3OS2: C, 51.96; H, 4.00; N, 15.15; S, 23.12; Found: C, 51.74; H, 3.89; N, 15.02; S, 23.00.

The Kazakh State Agrarian University, Department of Genetics, kindly presented seeds of spring wheat variety “Tabys 60” of Kazakhstan selection for biological assays. Lettuce seeds (Lactuca sativa L.), variety Iceberg Lettuce Regina Delle Ghiacciole and bent grass (Agrostis stolonifera KROMI) from “Agrofirma” were purchased from agriculture store.

The synthesized thioanhydrides (1a-g) were evaluated for growth-stimulating activity on the seeds of Kazakhstan selection spring wheat “Tabys 60” in the laboratory conditions. The screening was carried out in Petri dishes (25 seeds were placed in each dish) at room temperature 20 ± 5 °C, the incubation periods were 3 and 7 days, and the experiment was repeated 2 times. Stock solutions (0.1 and 0.01 mg/ml) of test compounds (1a-g) were prepared in water. In order to increase solubility in water, the test compounds were converted into hydrochloride salts. Aqueous solutions of the test compounds in the form of hydrochloride salts are hydrolytically stable. Wheat seeds were presoaked once by aqueous solutions (50 ml) of the test compounds for 2 h. The analysis of germination energy and capacity of wheat seeds was carried out by the standard methodology39. The values of germination energy and capacity were determined, respectively, on the 3rd and the 7th day of incubation. The number of germinated, swollen and dormant seeds was determined on the 3rd day of incubation. The number of all germinated seeds and roots, length, and mass of roots and shoots were measured on the 7th day of incubation. The mass of fresh roots and green shoots was weighed on an analytical scale. Preparations Akpinol KN-2 (1-methyl-4-hydroxy-4-[3-(naphthoxy)prop-1-ynyl]piperidine hydrochloride)40 and AN-16 (sodium N-(3-phenylprop-2-yn-1-yl)-N-butyldithiocarbamate)41 were used as the reference standards (0.1 and 0.01 mg/ml aqueous solutions) and water as the control standard.

The phytotoxic activity of the synthesized thioanhydride (2b) was screened for lettuce (Lactuca sativa) and bent grass (Agrostis stolonifera) in 24-well plates at room temperature 20 ± 5 °C. The effect of thioanhydride on the growth of the seedlings was observed after 7 days. The phytotoxicity was assessed on a scale ranging from 0 to 5, meaning no effect and complete inhibition, respectively42. Factors used in the evaluation include inhibition of root and shoot growth, as well as the overall appearance (i.e. presence of chlorotic and/or necrotic areas on the leaves). The herbicide 2.4-D was used as the standard. The tested solutions for compound (2b) as hydrochloride salt were prepared at various concentrations (0.1; 1; 0.02; 0.2; 2; 0.03; 0.3; 3 mg/ml) in water. Compounds (1c, 1 d) were tested at next concentrations 0,01; 0,03; 0,1; 0,3; 0,5; 1 mg/ml.

All data generated or analysed during this study are included in this published article (and its Supplementary Information files).

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We thank Olzhas Seylkhanov and Tulegen Seylkhanov for 1H and 13C NMR spectra recording and Bauyrzhan Bukenov for GCh MS spectra. This study was funded by the Science Committee of the Ministry of Science and Higher Education of the Republic of Kazakhstan; projects Nos. BR18574042 and AP09057956.

A.B. Bekturov Institute of Chemical Sciences, 106 Sh. Ualikhanov Str., Almaty, Kazakhstan

Yelena S. Sycheva, Meruyert S. Mukanova & Dariya B. Markina

Faculty of Chemistry and Chemical Technology, Al-Farabi Kazakh National University, 71 Al-Farabi Avenue, Almaty, Kazakhstan

Meruyert S. Mukanova & Dariya B. Markina

Institute of Botany and Phytointroduction, 36D/1 Timiryazev Str., Almaty, Kazakhstan

Gauhar S. Mukan

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Ye.S. and D.M. synthesized and purified all compounds. G.M. made biological screening and its analysis, prepared Figs. 1–2. M.M. analyzed and wrote the main manuscript text. All authors reviewed the manuscript.

Correspondence to Meruyert S. Mukanova.

The authors declare no competing interests.

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Sycheva, Y.S., Mukanova, M.S., Markina, D.B. et al. Synthesis and characterization of novel dithiocarbamic thioanhydrides and their application for plant growth stimulant and phytotoxic activity. Sci Rep 14, 24778 (2024). https://doi.org/10.1038/s41598-024-73260-8

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Received: 10 May 2024

Accepted: 16 September 2024

Published: 21 October 2024

DOI: https://doi.org/10.1038/s41598-024-73260-8

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