Synthesis, Structure and Acaricidal Activity of Tricyclohexyltin Benzoate①

ZHANG Zhi-Jian KUANG Dai-Zhi ZHANG Fu-Xing ZHU Xiao-Ming YU Jiang-Xi JIANG Wu-Jiu

?

Synthesis, Structure and Acaricidal Activity of Tricyclohexyltin Benzoate①

ZHANG Zhi-Jiana②KUANG Dai-ZhibZHANG Fu-XingbZHU Xiao-MingbYU Jiang-XibJIANG Wu-Jiub

a(421008)b(421008)

Tricyclohexyltin 4-amino-3-methyl-benzoate (1) and tricyclohexyltin 3,4-dime- thoxybenzoate (2) were synthesized and their crystal structures were determined by X-ray diffraction. Compound 1 belongs to the monoclinic system, space group21/with= 14.0554(15),= 11.6947(13),= 16.2720(17) ?,= 4,= 2565.7(5) ?3,D= 1.341 g·cm-3,(Mo) = 1.016 mm-1,(000) = 1080,= 0.0833 and= 0.2964. Compound 2 is of monoclinic system, space group2/with= 17.8712(6),= 8.4433(3),= 35.5783(13) ?,= 8,= 5366.8(3) ?3,D= 1.360 g·cm-3,(Mo) = 0.980 mm-1,(000) = 2288,= 0.0549,= 0.1279. In compounds 1 and 2, the central Sn atom is coordinated in a tetradentate manner to assume a distorted tetrahedral configuration. Preliminary biological tests showed that these two compounds have strong acaricidal activity.

organotin carboxylates, synthesis, crystal structure, acaricidal activity

1 INTRODUCTION

Organotin compounds have catalytic activity, bac- tericidal and anticancer effects and other various biological activities due to their structural diver- sity[1-5]. Wide researches about orgnanotin com- pounds have been made and many related reportshave been published[6-14]. Of organotin compounds, trialkyl-tin compounds attractscientists’ attention due to their stronginsecticidal, bactericidal and acaricidal activities[15, 16]. Organotin compounds show certain toxicity and side effects in their practical applications[17], and therefore organotin compounds of different structures were synthesized andwide researches were made on their structures and biological activities in order to reduce their toxicity. To date, significant results have been achieved[18-20].

In order to study further the influence of struc- tures of organotin compounds on their biological activities, we synthesized tricyclohexyltin 1 and 2, and then characterized them by elemental analysis, infrared spectra, and nuclear magnetic resonance (NMR) spectrometry. The two crystal structures were determined using X-ray single-crystal diffraction analysis, and acaricidal activities were also studied.

2 EXPERIMENTAL

2. 1 Reagents and instruments

All reagents used were chemically pure. Infrared spectrum (KBr) was recorded by FTIR-8700 in- frared spectrometer (Japan Shimadzu, 4000～400 cm-1). The elemental analysis was determined by PE-2400 (II) elemental analyzer. The crystal struc- ture was solved by BRUKER SMART APEX Ⅱ CCD single-crystal diffractometer.1H NMR spec- trum was determined by a BRUKER-400 NMR spectrometer. Melting point measurement was executed on an XT-4 binocular micromelting point apparatus without correction (Beijing Tektronix Instrument Co. Ltd.).

2. 2 Synthesis

The reaction scheme for synthesizing these two compounds is shown in Fig. 1

Fig. 1. Syntheses of the compounds

2. 2. 1 Synthesis of compound (1)

A mixture of tricyclohexyltin hydroxide 0.385 g (1 mmol) and 3-methyl-4-amino-benzoic acid 0.151 g (1 mmol) was refluxed with stirring in absolute ethanol (25 mL) and proper amount of triethylamine for 6 h. Most of the solvent was evaporated by vacuum. The reaction mixture was filtered, and the solid was recrystallized by absolute ethanol. The white crystals were collected. Yield: 0.388 g, 75%. m.p.: 215～216 ℃. Elemental analysis (C26H41NO2Sn): measured value (calculated value, %): C, 60.19 (60.24); H, 7.91 (7.97); N, 2.72 (2.70). IR(KBr): 3355.9 (m,N-H), 2916.2 (s,C-H), 1605.2 (s,as(COO)), 1311.5 (m,s(COO)), 478.3 (m,Sn-O), 416.6 (w,Sn-C) cm-1.1H NMR(CDCl3, ppm): 1.30～1.98 (m, 33H, Cy-), 3.92(s, 2H,-N2), 6.63～7.80(m, 3H, Ph-), 2.18(s, 3H, Ph-C3).

2. 2. 2 Synthesis of compound (2)

A mixture of tricyclohexyltin hydroxide (0.385 g, 1 mmol) and 3-methyl-4-amino-benzoic acid (0.182 g, 1 mmol) was refluxed with stirring in absolute ethanol (25 mL) and proper amount of triethylamine for 6 h. Most of the solvent was evaporated by vacuum. The reaction mixture was filtered, and the solid was recrystallized by absolute ethanol. The white crystals were collected. Yield: 0.43 g, 78%, m.p.: 251～252 ℃. Elemental analysis (C27H42O4Sn): measured value (calculated value, %): C, 59.06 (59.03); H, 7.69 (7.71). IR(KBr): 2916.2 (m,C-H), 1627.8 (s,as(COO)), 1315.4 (m,s(COO)), 491.8 (m,Sn-O), 418.5 (w,Sn-C) cm-1.1H NMR (CDCl3, ppm): 1.30～1.98 (m, 33H, Cy-), 3.92 (s, 2H,-N2), 6.63～7.80 (m, 3H, Ph-), 2.18 (s, 3H, Ph-C3).

2. 3. 1 Structural determination for compound 1

A crystal of compound 1 with proper size was chosen for data collectionwhich was performed on a Bruker SMART APEX II CCD diffractometer equip- ped with a graphite-monochromatic Moradiation (= 0.71073 nm) using ascan mode.At 296(2) K, a total of 21495 reflections were collected in the range of 1.5≤27.58°, including 5880 independent ones (int= 0.0246) and 5401 observed ones (> 2()). All the data were corrected byfactors and empirical absorbance. The structure was solved by direct methods. All non-hydrogen atoms were deter- mined in successive difference Fourier synthesis, and all hydrogen atoms were added according to theoretical models. All hydrogen and non-hydrogen atoms were refined by their isotropic and anisotropic thermal parameters through full- matrix least-squares techniques. The final= 0.0883,= 0.2964, (Δ)max= 2.771 and (Δ)min= –2.653 e·nm-3. All calculations were completed by the SHELXTL-97 program.

2. 3. 2 Structural determination of compound 2

A crystal of compound 2 with proper dimensions was chosen for data collection which was performed on a Bruker SMART APEX II CCD diffractometer equipped with a graphite-monochromatic Mora- diation (= 0.71073 nm) using ascan mode. At 296(2) K, a total of 19987 reflections were collected in the range of 1.15≤≤25°, of whcih 4722 were independent (int= 0.0303) and 3847 were observed (> 2()). All the data were corrected byfactor and empirical absorbance. The crystal structure was solved by direct methods. All non-hydrogen atoms were determined in successive difference Fourier synthesis, and all hydrogen atoms were positioned geometrically. All hydrogen and non-hydrogen atoms were refined by their isotropic and anisotropic thermal parameters through full-matrix least-squares method. The final= 0.0549,= 0.1279, (Δ)max= 1.450 and (Δ)min= –1.231 e·nm-3. All calculations were completed by SHELXTL-97 program.

2. 4 Acaricidal activity

Compounds 1 and 2,0.1 g for each, were respec- tively dissolved in the mixed solvent of absolute ethanol-xylene (v/v = 1:1). 1 mL of tween-80 was added as emulsifier to each of the above 2 solutions. Then the above mixed solvent was added to each of the 2 solutions to make their component con- centration be 10% with a constant volume of 10 mL for test. Each of the above prepared solutions was diluted with water at the ratio of 1:4 to prepare a solution series whose component concentration was 200.00, 50.00, 12.50, 3.12, and 0.78 μg·mL-1, respectively. Panonychus citri were soaked in each of the above solutions to test the acaricidal activity of those 2 compounds. The mortality of acarids was calculated by examining the dead acarids in test solution and comparing with the blank solution 24 h later.

3 RESULTS AND DISCUSSION

3. 1 Crystal structure

The selected bond lengths and bond angles of compounds 1 and 2 are listed in Tables 1 and 2, respectively. The molecular structures of 1 and 2 are shown in Figs. 2 and 3, and their packing dia- grams in Figs. 4 and 5, respectively. The molecular structures and structural parameters both show that 1 and 2 are monomers.

Table 1. Selected Bond Lengths (?) and Bond Angles (°) of Compound 1

Table 2. Selected Bond Lengths (?) and Bond Angles (°) for Compound 2

Fig. 2. Crystal structure of compound 1

Fig. 3. Crystal structure of compound 2

Fig. 4. Crystal packing diagram of compound 1

Fig. 5. Crystal packing diagram of compound 2

The molecular structure of compound 1 resulted from the coordination of tricyclohexyltin with 3-me- thyl-4-amino-benzoic acid. In 1, the asymmetric and symmetric stretching vibrations of the carbonyl group are as follows:as(COO)= 1605.2 ands(COO)= 1311.5 cm-1, Δ= 293.7 cm-1. Asas(COO)shifts neither remarkably to the low nor to the high region, the tricyclohexyltin may be coordinated with the oxygen of carbonyl group only in a monodentate manner. The bond lengths of Sn(1)-C(8) (2.160(10) ?), Sn(1)-C(14) (2.171(10) ?) and Sn(1)-C(20) (2.152(12) ?) are close to each other; and the Sn(1)-O(1) bond is 2.073(8) ?. The C(20)-Sn(1)-C(8), C(20)-Sn(1)-C(14), C(8)-Sn(1)-C(14), O(1)-Sn(1)-C(20), O(1)-Sn(1)-C(8), and O(1)-Sn(1)-C(14)bond angles are 116.6(4), 114.4(4), 113.1(4), 106.1(4), 108.6(4) and 95.2(3)o correspondingly, differing from those (0.68～14.08o) found in regular tetrahedra.

The molecular structure of compound 2 is cons- tructed through the coordination of tricyclohexyltin with 3,4-dimethoxy-benzoic acid. In 2, the asym- metrical stretching vibration of carbonyl group isas(COO)= 1627.8cm-1, and the symmetrical stre- tching vibration iss(COO)= 1315.4 cm-1, with Δ= 312.4 cm-1, so we can see that the carbonyl group coordinates in a monodentate fashion. The Sn(1)-C(10) (2.171(4)?), Sn(1)-C(16) (2.182(3)?) and Sn(1)-C(22) (2.155(2)?) are close to each other; the bond Sn(1)-O(1) is 2.0629(14)?. The bond angles of C(22)-Sn(1)-C(10), C(22)-Sn(1)-C(16), C(10)-Sn(1)-C(16), O(1)-Sn(1)-C(22), O(1)-Sn(1)-C(10), and O(1)-Sn(1)-C(16) are 109.72(13), 124.23(11), 115.42(16), 106.61(7), 92.63(12) and 102.36(10)o in turn, deviating from the value of 2.67～16.65o for a regular tetrahedron.

The above structural analyses demonstrate that the central Sn atoms in compounds 1 and 2 both adopt deformed tetrahedral geometries[21, 22].

3. 2 Acaricidal activity

The mortality of panonychus citri in different solutions was measured by Abbott formula, and the result is shown in Table 3. Both compounds 1 and 2 possess higher acaricidal activities. For either of them, a 50 μg·mL-1solution may kill at least 90% of the acarids, and compound 1 has higher acaricidal activity than 2.

Table 3. Corrected Morality of Panonychus Citri in the Solution of Compounds 1 and 2 of Different Concentration 24 h Later (%)

Two tricyclohexyltin compounds, 1 and 2, show higher acaricidal activities, so they may be worth further study for wide applications. Other biological activities of 1 and 2 remain to be further researched.

(1) Van Lanen, S. G.; Dorrestein, P. C.; Christenson, S. D.; Liu, W.; Ju, J. H.; Kelleher, N. L.; Shen, B. Biosynthesis of the beta-amino acid moiety of the enediyne antitumor antibiotic C-1027 featuring beta-amino acyl-S-carrier protein intermediates.2005, 127, 11556-11557.

(2) Molter, A.; Kalu?erovi?, G. N.; Kommera, H.; Paschke, R.; Langer, T.; P?ttgen, R.; Mohr, F. Synthesis, structures, 119Sn M?ssbauer spectroscopic studies and biological activity of some tin(IV) complexes containing pyridyl functionalised selenosemicarbazonato ligands.2012, 701, 80-86.

(3) Xie, Q. L.; Xu, X. H.; Wang, H. G.;Zhang, Z. G.; Hu, J. M.; Wang, H. G.; Yao, X. K.; Wang, R. J. The crystal and molecular structures of tribenzyltin and tributyltin 5-tertbutyl furoate.1991, 49, 1085-1093.

(4) Dang, Y. Q.; Yang, H. J.; Tian, L. J. Syntheses and structural characterization of dimethyltin complexes of-(3-Methoxysalicylidene)--amino acid.2012, 31, 479-484.

(5) Chandrasekhar, V.; Narayanan, R. S.; Thilagar, P. Organostannoxane-supported palladium nanoparticles. Highly efficient catalysts for Suzuki-coupling reactions.2009, 28, 5883-5888.

(6) Chandrasekhar, V.; Gopal, K.; Singh, P. Narayanan, R. S.; Duthie, A.Self-assembly of organostannoxanes: formation of gels in aromatic solvents.2009, 28, 4593-4601.

(7) Kuang, D. Z.; Feng, Y. L.; Zhang, F. X.; Wang, J. Q. Synthesis, crystal structure and quantum chemistry of the organooxotin cluster [(-O)(-OH)Sn2(-Bu)4]2(C5H4NCO2)2.. 2010, 26, 2160-2164.

(8) Zhang, F. X.; Wang, J. Q.; Kuang, D. Z.; Feng, Y. L.; Zhang, Z. J.; Xu, Z. F.; He, P. Synthesis, crystal structure and quantum chemistry of the ladder bis(-methylbenzyl)tin oxo(chlo) cluster.2009, 25, 213-217.

(9) Deng, Y. F.; Chen, M. S.; Zhang, C. H.; Kuang, D. Z.; Nie, X. Synthesis, crystal structure and biological activity of drum organooxotin cluster [nBuSn(O)(NNA)]6..2009, 25, 2229-2232.

(10) Chandrasekhar, V.;Nagendran, S.; Bansal, S.; Cordes, A. W.; Vij, A. Rangoli with tin drums: C-H···O bond-assisted supramolecular grids involving organostannoxane clusters.2002, 21, 3297-3300.

(11) Chandrasekhar, V.; Sasikumar, P.; Thilagar, P. Formation of a double-bicapped hexatin phosphate cage by a de-arylation reaction. Synthesis and structure of [(PhSn)6(-OH)2(3-O)2(-OEt)4{(ArO)PO3}4] (Ar = 2,6-i-Pr2C6H3).2007, 26, 4386-4388.

(12) Chandrasekhar, V.; Baskar, V.; Gopal, K.; Vittal, J. J.Organooxotin cages, {[(n-BuSn)3(3-O)(OC6H4-4-X)3]2}, X = H, Cl, Br and I, in double O-capped structures: halogen-bonding-mediated supramolecular formation.2005, 24, 4926-4932.

(13) Chandrasekhar, V.; Baskar, V.; Steiner, A.; Zacchini, S. Reactions of n-Bu2SnO and (n-Bu3Sn)2O with 1,1,2,2,3-pentamethyltrimethylene phosphinic acid: synthesis and X-ray crystal structures of a novel spirocyclic coordination polymer and a 16-membered inorganic macrocycle.2004, 23, 1390-1395.

(14) Chandrasekhar, V.; Baskar, V.; Steiner, A.;Zacchini, S. Synthesis of a tetranuclear organooxotin cage by debenzylation reactions: X-ray crystal structure of [(Ph2CH2)2Sn2O(O2P(OH)-t-Bu)4]2.2002, 21, 4528-4532.

(15) Liu, H. Y.; Lin, S. Studies process for bioactivity of trialkyltin compounds.2004, 18, 14-18.

(16) Eng, G.; Song, X.; Zapata, A.; Dios, A. C.; Casabianca, L.; Pike, R. D. Synthesis, structural and larvicidal studies of some triorganotin 2-(-chlorophenyl)-3-methylbutyrates.. 2007, 692, 1398-1404.

(17) Fargasová, A. Comparative study of ecotoxicological effect of triorganotin compounds on various biological subjects.1997, 36, 38-42.

(18) Basl, T. S. Antimicrobial activity of organotin(IV) compounds: a review.. 2008, 22, 195-204.

(19) Aminim, M.; Azadmehr, A.; Alijani, V.; Khavasi, H. R.; Hajiashrafi, T.; Kharat, A. N.Di- and triorganotin(IV) carboxylates derived from triorganotin(IV) iodide with mixed organic groups on tin: cyclic, hexameric triorganotin(IV) carboxylates.. 2008, 362, 355-360.

(20) Tzimopoulos, D.; Sanidasi, I.; Varvogli, A. C.; Czapik, A.; Gdaniec, M.; Nikolakaki, E.; Akrivos, P. D. On the bioreactivity of triorganotin aminobenzoates. Investigation of trialkyl and triarylyltin(IV) esters of 3-amino and 4-aminobenzoic acids.2010, 104, 423-430.

(21) Luo, N; Sun, L. J.; Liu, Z. Z.; Xie, Q. L.; Mu, Z. D. Synthesis, characterization and biological activities of trialkyltin(IV) ferrocene carboxylates.2000, 17, 154-158.

(22) Xie, Q. L.; Xu, X. H.; Zhang, D. K. Synthesis and structure analysis of trlbenzyltin carboxylates.1992, 50, 508-514.

15 December 2013;

11 July 2014 (CCDC 880578 and 844047)

① This research was supported by the Natural Science Foundation of Hunan Province (No.13JJ3112), Scientific & Technological Projects of Hunan Province (No. 2014FJ3060), the Open Fund Project of Key Laboratory in Hunan Universities (No.13K105), Scientific Research Fund of Hunan Provincial Education Department of China (No.12C0537), the Construct Program of the Key Discipline in Hunan Province, Scientific & Technological Projects of Hengyang city (2011KG56, 2012KJ30), Science Foundation of Hengyang Normal University (No.12C45) and the Youth Backbone Teacher Training Program of Hengyang Normal University (2012)

. Zhang Zhi-Jian, male, lecturer, majoring in biochemistry. E-mail: zjzhang.cn@gmail.com