Synthesis of novel 2,5-disubstituted-1,3,4-selenadiazoles from fatty acid hydrazides

Himani Varshney; Aiman Ahmad; Abdul Rauf

doi:10.1016/j.arabjc.2014.08.002

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Original article

11 (

); 143-148

doi:

10.1016/j.arabjc.2014.08.002

Synthesis of novel 2,5-disubstituted-1,3,4-selenadiazoles from fatty acid hydrazides

Himani Varshney, Aiman Ahmad, Abdul Rauf^⁎

Department of Chemistry, Aligarh Muslim University, Aligarh 202002, India

⁎Corresponding author. Address: Department of Chemistry, University Road, Aligarh Muslim University, Aligarh 202002, India. Mobile: +91 9412545345. abduloafchem@gmail.com (Abdul Rauf)

Received: 2013-7-12, Accepted: 2014-8-6, Published: 2014-01-01

Disclaimer:
This article was originally published by Elsevier and was migrated to Scientific Scholar after the change of Publisher.

Peer review under responsibility of King Saud University.

Abstract

A series of novel unsaturated hydroxy and non-hydroxy fatty acid residue substituted 1,3,4-selenadiazoles were described here. These derivatives were synthesized from the reaction of fatty acid hydrazide 1(a–d) with acetyl chloride in the presence of anhydrous sodium carbonate in tetrahydrofuran and water at 0 °C, to form N′-acetyl undec-10-enoic hydrazide 2a, N′-acetyl-(9Z)-octadec-9-enoic hydrazide 2b, N′-acetyl-(9Z, 12R)-12-hydroxy-9-enoic hydrazide 2c, and N′-acetyl-(9R, 12Z)-9-hydroxy-12-enoic hydrazide 2d. Then these hydrazines (dicarbonyl compound) on reaction with Woollin’s reagent (WR) in toluene led to the corresponding 2-(dec-9′-enyl)-5-methyl-1,3,4-selenadiazole 3a, 2-[(8′Z)-heptadec-8′-enyl]-5-methyl-1,3,4-selenadiazole 3b, 2-[(8′Z, 11′R)-11′-hydroxy-octadec-8′-enyl)]-5-methyl-1,3,4-selenadiazole 3c, and 2-[(8′R, 11′Z)-8′-hydroxy-octadec-11′-enyl)]-5-methyl-1,3,4-selenadiazole 3d, respectively. These synthesized compounds were characterized on the basis of IR, ¹H NMR, ¹³C NMR, mass spectra and elemental analysis results.

Keywords

Hydrazine

Woollin’s reagent

Selenadiazole

Fatty acid hydrazide

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1 Introduction

The first organo selenium compound diethyl selenide was synthesized in 1836 (Löwig, 1836). The selenoheterocyclic compounds are closely related to the sulfur compounds but their properties are quite different from the sulfur compounds. A number of hetero organo selenium compounds (Mlochowski et al., 2007), such as isoselenazole, selenosulfide, selenadiazoles, and selenatriazoles, have been known from the literature.

Organo selenium compounds found its application in various fields such as organic synthesis (Patai and Rappoport, 1986; Back, 1994), ligand chemistry (Hope and Levason, 1993), material synthesis (Bochman, 1996), biochemistry (Burk, 1994), photography (Yamashita et al., 1994) and biologically relevant processes. In the organic synthesis, the organo selenium compounds can be used as an electrophile or as nucleophile for functional group manipulation in a variety of substrates under mild condition (Paulmier, 1986) and also utilized in modern asymmetric synthesis, which have generated a new trend in organo selenium chemistry (Wirth, 1999). In biochemistry field, the selenium atom is incorporated in the selenocystine residues in various enzymes such as tetraiodo thyronine-5′-deiodinase, formate dehydrogenase, glycine reductase, glutathione peroxidase, plasma protein P (Böck, 1994) and hydrogenase, where it has been found to act as more reactive nucleophile than their sulfur counterparts. Sometimes organo selenium compounds are also used as selenoenzyme [mimics of glutathione peroxidase (GPx)], that protects the cell membrane from oxidative damage and helps in the reduction of various hydroperoxides (Mugesh and Singh, 2000).

In addition to these chemical properties, substituted organo selenium compounds also show a number of biological properties (Prabakaran et al., 2011), good electro optical properties (Velusamy et al., 2005), electroluminescent (Yang et al., 2005), and non linear optic potential candidates for two photon absorption and sensor application (Ostrowski et al., 2003). Substituted selenadiazole derivatives have been reported to possess cytotoxic (Jalilian et al., 2003), and antiproliferative activities as well. These compounds are found to be active against various types of cancer cells such as colon (HT-29), breast (MCF-7), lung (HTB-54) and leukemia (CCRF-CEM) (Plano et al., 2010) and also active against HIV-I replication in MT₄-cells (Zhan et al., 2009). Apart from the above mentioned biological properties selenadiazoles, have also been found to possess anticonvulsant, antitumor, antiinflammatory, analgesic, antibacterial, fungicidal (Shealy and Clayton, 1967; Padmavathi et al., 2009; Parveen et al., 2009; El Sadek et al., 2013 ) and pesticidal activities.

1,2,4-Aryl selenadiazoles can be obtained by the reaction of selenocarboxamides in the presence of iodine (Becker and Meyer, 1904; Cohen, 1978; Dotsenko et al., 2013 ) and substituted 1,3,4-selenadiazoles can be synthesized from the reaction of N,N′-diaryloxalodihydrazonoyldichlorides with potassium selenocyanate (Farag et al., 1994), but the selenocarboxamide gives better yield and less reaction time in the presence of palladium catalyst (Al-Rubaie et al., 2002). Substituted and Multi-arm/Multiple 1,2,3-selenadiazole rings have been prepared by the reaction of selenium dioxide with α-ketomethylene semicarbazones or hydrazones in the presence of acetic acid (Saravanan et al., 2007; Al-Smadi and Ratrout, 2005; Al-Smadi and Al-Momani, 2008 ). The synthesis of 1,2,3-selenadiazoles under ultrasonic and microwave irradiation has also been reported in the literature (Shinde et al., 2010). 3,5-Diaryl-1,2,4-selenadiazoles have been synthesized from selenoamides (Rong and Sen, 2002), these selenoamides are not only useful for the synthesis of selenium-nitrogen heterocycles but also for the reaction with various organic and inorganic reagents because of the high reactivity of their carbon selenium double bond. The selenadiazoles are utilized in the synthesis of cadmium selenide (Khanna et al., 2004), which is an important semi conductor that can act as optoelectronic material. Here, we are generally focusing on the synthesis of 2,5-disubstituted-1,3,4-selenadiazoles. A number of methods have been reported for their syntheses, all these methods are limited due to some consequences. But 2,4-diphenyl-1,3-diselenadiphosphetane-2,4-diselenide (Hua et al., 2009) [PhP(Se)(μ-Se)]₂, is found to be the more appropriate reagent in every aspect for the synthesis of 2,5-disubstituted-1,3,4-selenadiazoles, although WR is very useful in the synthesis of a wide variety of cyclic and acyclic selenium containing compounds (Hua et al., 2013).

The fatty acid organo selenium compounds were synthesized earlier (Agarwal et al., 1990; Saeed et al., 1991) from our laboratory. In this paper, we report the synthesis of fatty acid residue substituted 1,3,4-selenadiazoles with Woollin’s reagent (WR) through the corresponding 1,2-dicabonyl compound selenation.

2 Results and discussion

We report the synthesis of 2-alkenyl/hydroxy alkenyl-5-alkyl-substituted-1,3,4-selenadiazole 3(a–d), from the corresponding intermediate N′-acetyl fatty acid hydrazide 2(a–d), on reaction with Woollin’s reagent in dry toluene. These substituted hydrazides 2(a–d), were synthesized by the reaction of fatty acid hydrazide 1(a–d), with acetyl chloride in THF/H₂O solvent in the presence of anhydrous Na₂CO₃ at 0 °C. The synthetic pathway for the synthesis of substituted fatty acid hydrazides 2(a–d) and 2,5-disubstituted 1,3,4-selenadiazoles 3(a–d), is presented in Scheme 1 and proposed mechanism of the reaction was also described. All the synthesized compounds were purified by column chromatography and characterized by IR, ¹H NMR, ¹³C NMR elemental analyses and mass spectra. The detailed spectral description of compound 2(a) is given below.

Synthesis of novel 2,5-disubstituted 1,3,4-selenadiazoles.

The IR spectrum of the compound showed characteristic peaks at 3314, 3219 cm⁻¹ (N⚌H stretching), 1628 cm⁻¹ (C⚌O stretch) and at 1265 cm⁻¹ (N—N stretch). The ¹H NMR spectra of the compound showed some diagnostic peaks. Two singlets were observed at δ 9.07, 8.82 for two N—H stretching. The methine proton of C₁₀ showed a signal at δ 5.79. The methylene protons designated as H_b and H_a, displayed two distinct δ values when coupled with adjacent C₁₀ methine protons. Thus, spectra showed two doublets at δ 4.98, 4.92 and a sharp singlet at δ 2.17 for methyl protons. The ¹³C NMR spectra showed peaks at δ 174.2, 172.1 for carbonyl carbon and at 18.5 for methyl carbon adjacent to carbonyl carbon. Elemental analysis result and molecular formula were also consistent with the mass spectra. The characterization data of compound 3(a) are discussed below.

The IR spectrum of compound 3(a), showed characteristic peaks at 1461 cm⁻¹ (C⚌N stretch), 1268 cm⁻¹ (N—N stretch), and 1082 cm⁻¹ (C—N stretch). The ¹H NMR spectra of the compound showed some diagnostic peaks. The methine proton C₉ showed a signal at δ 5.80, the methylene protons H_b and H_a showed two separate doublets at δ 4.99, 4.93 respectively and a sharp singlet at δ 2.10 for methyl protons. The ¹³C NMR spectra showed diagnostic peaks at δ 168.8, 158.7 for ring carbons. Elemental analysis showed the significant results. A mass spectrum of the compound was also consistent with assigned molecular formula.

3 Experimental

3.1

3.1 Physical measurements

Undec-9-enoic acid (98%) and (9Z)-octadec-10-enoic acid (97%) were purchased from the Fluka Chemicals, Switzerland. (9Z, 12R)-12-Hydroxy-octadec-9-enoic (Ricinolic) and (9R, 12Z)-9-hydroxy-octadec-12-enoic (Isoricinolic) acids were isolated from the naturally occurring Wrightia tinctoria seeds by standard extraction procedure (Gunstone, 1954). The solvents used for the extraction procedure, were purified by the normal distillation process. Woollin’s reagent was commercially available and purchased from Sigma Aldrich, USA.

The fatty chain substituted 1,3,4-selenadiazole derivatives were synthesized by adopting the reported procedure (Hua et al., 2009). The purity of the newly synthesized compounds was tested on glass plates coated with silica gel G (for thin layer chromatography) and purification of the synthesized compounds was carried out by column chromatography with silica gel (mesh 60–120 for column chromatography), purchased from Merck, Mumbai. The melting points were determined on an electro thermal digital melting point apparatus on glass cover slips and are uncorrected. Infrared spectra (IR) were recorded as KBr-pellets on a FT-IR spectrometer in cm⁻¹. The ¹H NMR and ¹³C NMR spectra were recorded on a Bruker Avance II-400 spectrometer in CDCl₃ using Me₄Si (TMS, Tetramethylsilane) as standard. Chemical shifts were recorded in δ (delta) units. Mass spectra were recorded on a Jeol SX-102/DA-600 (FAB) spectrometer.

3.2

3.2 General procedure for the synthesis of fatty acid hydrazides 1(a–d)

Fatty acid hydrazides were synthesized from the literature reported method (Rauf et al., 2007), previously synthesized in our laboratory.

3.3

3.3 General procedure for the synthesis of dialkyl hydrazines/substituted fatty acid hydrazides 2(a–d)

A suspension of fatty acid hydrazides (0.01 mol) and anhydrous sodium carbonate (0.01 mol) was prepared in 60 mL of tetrahydrofuran (THF) and 60 mL of water. This suspension was gradually added to a continuously stirred solution of acetyl chloride (0.11 mol) in 30 mL of THF at 0 °C. The reaction was stirred at 0 °C for 4–5 h and then at room temperature for 8 h. A precipitate was obtained, which was then separated out by filtration and wash the precipitate 2–3 times with cold THF, then with the diethyl ether and finally dried in vacuum. Spectral description of the newly synthesized compounds was given below.

3.3.1

3.3.1 N′-Acetyl undec-10-enoic hydrazide 2(a)

White powder; Yield: 74%; m.p. 98–99 °C; IR (KBr, cm⁻¹): 3314, 3219 (N—H stretch), 2913 (C—H asymm.), 2850 (C—H symm.), 1628, 1588 (C⚌O), 1265 (N—N stretch), 1183 (C—C aliphatic), 1082 (C—N stretch); ¹H NMR (400 MHz, CDCl₃, δ, ppm): 9.07, 8.82 (s, 1H, NH—NH), 5.79 (tdd, 1H, $J_{H —^{9} {CH}_{2}}$ = 5.7 Hz, $J_{H — H_{a}}$ = 9.0 Hz, $J_{H — H_{b}}$ = 15.7 Hz, CH₂⚌CH), 4.98 (dd, 1H, $J_{Ha — H}$ = 9.0 Hz, $J_{H_{a} — H_{b}}$ = 1.0 Hz, H_aC⚌CH), 4.92 (dd, 1H, $J_{H_{b} — H}$ = 15.7 Hz, $J_{H_{b} — H_{a}}$ = 1.0 Hz, H_bC⚌CH), 2.25 (t, 2H, J = 7.5 Hz, CH₂CO), 2.17 (s, 3H, COCH₃), 2.03 (m, 2H, ⚌CHCH₂), 1.63 (m, 2H, ⚌CH₂CH₂CO), 1.34 (br.s, 10H, CH₂(CH₂)₅); ¹³C NMR (100 MHz, CDCl₃, δ, ppm): 174.2, 172.1, 128.9, 128.1, 37.1, 36.9–20.9, 18.5; MS (ESI): m/z = 263.1 [M+Na]⁺, Calculated = 263.2. Analysis found: C, 64.77; H, 9.99; N, 11.43%. C₁₃H₂₄N₂O₂ requires C, 64.97; H, 10.04; N, 11.65%.

3.3.2

3.3.2 N′-Acetyl-(9Z)-octadec-9-enoic hydrazide 2(b)

White powder; Yield: 76%, m.p. 123 °C; IR (KBr, cm⁻¹): 3322, 3228 (N—H stretch), 2924 (C—H asymm.), 2852 (C—H symm.), 1633, 1598 (C⚌O), 1282 (N—N stretch), 1176 (C—C aliphatic), 1094 (C—N stretch); ¹H NMR (400 MHz, CDCl₃, δ, ppm): 9.20, 8.53 (s, 1H, NH—NH), 5.26 (m, 2H, CH⚌CH), 2.67 (t, 2H, J = 7.6 Hz, CH₂CO), 2.10 (s, 3H, COCH₃), 2.02 (m, 4H, CH₂CH⚌CHCH₂), 1.93 (m, 2H, CH₂CH₂CO⚌), 1.62 (m, 2H, CH₂CH₃), 1.26 (br.s, 18H, (CH₂)₉), 0.80 (dis.t, 3H, CH₂CH₃); ¹³C NMR (100 MHz, CDCl₃, δ, ppm): 175.1, 173.5, 131.2, 129.5, 36.9, 35.4–21.5, 18.1, 14.6; MS (ESI): m/z = 361.5 [M+Na]⁺, Calculated = 361.4. Analysis found: C, 70.67; H, 11.09; N, 8. 17%. C₂₀H₃₈N₂O₂ requires C, 70.97; H, 11.29; N, 8.27%.

3.3.3

3.3.3 N′-Acetyl-(9Z, 12R)-12-hydroxy-octadec-9-enoic hydrazide 2(c)

White powder; Yield: 65–70%; m.p. 119 °C; IR (KBr, cm⁻¹): 3320, 3236 (N—H stretch), 2920 (C—H asymm.), 2852 (C—H symm.), 1631, 1598 (C⚌O), 1272 (N—N stretch), 1166 (C—C aliphatic), 1041 (C—N stretch); ¹H NMR (400 MHz, CDCl₃, δ, ppm): 9.15, 8.67 (s, 1H, NH—NH), 5.40 (m, 2H, CH⚌CH), 3.78 (m, 1H, CHOH), 2.36 (t, 2H, J = 7.6 Hz, CH₂CO), 2.12 (s, 3H, COCH₃), 2.05 (m, 4H, CH₂CH⚌CHCH₂), 1.98 (m, 1H, CHOH), 1.64 (m, 2H, CH₂CH₂CO), 1.60 (m, 2H, CH₂CHOH), 1.30 (br.s, 16H, (CH₂)₈), 0.89 (dis.t, 3H, CH₂CH₃); ¹³C NMR (100 MHz, CDCl₃, δ, ppm): 176.0, 175.2, 130.8, 130.1, 71.5, 36.2, 35.1–20.9, 18.9, 13.8; MS (ESI): m/z = 377.4 [M+Na]⁺, Calculated = 377.4. Analysis found: C, 67.67; H, 10.69; N, 7. 89%. C₂₀H₃₈O₃N₂ requires C, 67.77; H, 10.78; N, 7.90%.

3.3.4

3.3.4 N′-Acetyl-(9R, 12Z)-9-hydroxy-octadec-12-enoic hydrazide 2(d)

Light yellow powder; Yield: 72%; m.p. 122 °C; IR (KBr, cm⁻¹): 3326, 3238 (N—H stretch), 2925 (C—H asymm.), 2848 (C—H symm.), 1627, 1578 (C⚌O), 1299 (N—N stretch), 1170 (C—C aliphatic), 1054 (C—N stretch); ¹H NMR (400 MHz, CDCl₃, δ, ppm): 9.23, 8.63 (s, 1H, NH—NH), 5.42 (m, 2H, CH⚌CH), 3.75 (m, 1H, CHOH), 2.35 (t, 2H, J = 7.5 Hz, CH₂CO), 2.16 (s, 3H, COCH₃), 2.07 (m, 4H, CH₂CH⚌CHCH₂), 1.90 (m, 1H, CHOH), 1.59 (m, 2H, CH₂CH₂CO), 1.48 (m, 2H, CH₂CHOH), 1.31 (br.s, 16H, (CH₂)₈), 0.88 (dis.t, 3H, CH₂CH₃); ¹³C NMR (100 MHz, CDCl₃, δ, ppm): 177.2, 176.8, 132.3, 131.4, 72.4, 38.7, 32.5–25.4, 17.8, 14.0; MS (ESI): m/z = 377.5 [M+Na]⁺, Calculated = 377.4. Analysis found: C, 67.64; H, 10.59; N, 7.79%. C₂₀H₃₈O₃N₂ requires C, 67.77; H, 10.78; N, 7.90%.

3.4

3.4 General procedure for the synthesis of 2,5-disubstituted-1,3,4-selenadiazoles 3(a–d)

An equimolar mixture of hydrazine derivatives (2) (0.01 mol) and Woollin’s reagent (WR) (0.01 mol) in dry toluene, was refluxed for 12 h. The red suspension was obtained, which was disappeared on refluxing. Finally a brown suspension was obtained along with the gray metal selenium. Progress of the reaction was monitored by TLC. After completion of the reaction, the reaction mixture was cooled to room temperature and removed the excess of toluene by drying the suspension in vacuum. After that, the residue was dissolved in dichloromethane and purified by column chromatography (with appropriate eluent), to give the target product as oily liquid. For the calculation of molecular weight, the most abundant isotope of selenium [⁸⁰Se, Mol. wt: 79.997] is taken. Spectral description of the newly synthesized compounds was given below.

3.4.1

3.4.1 2-(Dec-9′-enyl)-5-methyl-1,3,4-selenadiazoles 3(a)

Oily liquid; Yield: 64%; IR (KBr, cm⁻¹): 2919 (C—H asymm.), 2852 (C—H symm.), 1461 (C⚌N), 1163–808 (C—C aliphatic), 1268 (N—N stretch), 1082 (C—N stretch); ¹H NMR (400 MHz, CDCl₃, δ, ppm): 5.80 (tdd, 1H, $J_{H —^{9} {CH}_{2}}$ = 5.9 Hz, $J_{H — H_{a}}$ = 9.2 Hz, $J_{H — H_{b}}$ = 16.0 Hz, CH₂⚌CH), 4.99 (dd, 1H, $J_{H_{a} — H}$ = 9.2 Hz, $J_{H_{a} — H_{b}}$ = 1.2 Hz, H_aC⚌CH), 4.93 (dd, 1H, $J_{H_{b} — H}$ = 16.0 Hz, $J_{H_{b} — H_{a}}$ = 1.2 Hz, H_bC⚌CH), 2.77 (t, 2H, J = 7.6 Hz, CH₂C⚌N), 2.10 (s, 3H, ⚌CCH₃), 1.94 (m, 2H, ⚌CHCH₂), 1.75 (m, 2H, CH₂CH₂C⚌N), 1.27 (br.s, 10H, CH₂(CH₂)₅); ¹³C NMR (100 MHz, CDCl₃, δ, ppm): 168.8, 158.7, 129.9, 128.8, 36.3, 35.5–22.4, 17.5; MS (ESI): m/z = 309.2 [M+Na]⁺, Calculated = 309.1. Analysis found: C, 54.45; H, 7.69; N, 9. 69%. C₁₃H₂₂N₂Se requires C, 54.55; H, 7.73; N, 9.78%.

3.4.2

3.4.2 2-[(8′Z)-Heptadec-8′-enyl]-5-methyl-1,3,4-selenadiazoles 3(b)

Oily liquid; Yield: 66%; IR (KBr, cm⁻¹): 2927 (C—H asymm.), 2855 (C—H symm.), 1457 (C⚌N), 1171–790 (C—C aliphatic), 1278 (N—N stretch), 1084 (C—N stretch); ¹H NMR (400 MHz, CDCl₃, δ, ppm): 5.15 (m, 2H, CH⚌CH), 2.27 (t, 2H, J = 7.4 Hz, CH₂C⚌N), 2.10 (s, 3H, ⚌CCH₃), 2.01 (m, 4H, CH₂CH⚌CHCH₂), 1.46 (m, 2H, CH₂CH₂C⚌N), 1.18 (br.s, 20H, (CH₂)₁₀), 0.82 (dis.t, 3H, CH₂CH₃); ¹³C NMR (100 MHz, CDCl₃, δ, ppm): 167.1, 159.2, 134.2, 133.3, 37.0, 36.8–20.5, 18.0, 14.2; MS (ESI): m/z = 407.3 [M+Na]⁺, Calculated = 407.4. Analysis found: C, 62.45; H, 9.36; N, 7. 13%. C₂₀H₃₆N₂Se requires C, 62.49; H, 9.42; N, 7.28%.

3.4.3

3.4.3 2-[(8′Z, 11′R)-11′-Hydroxy-octadec-8′-enyl)]-5-methyl-1,3,4-selenadiazoles 3(c)

Yellow oily liquid; Yield: 65%; IR (KBr, cm⁻¹): 2924 (C—H asymm.), 2852 (C—H symm.), 1458 (C⚌N), 1169–798 (C—C aliphatic), 1254 (N—N stretch), 1094 (C—N stretch); ¹H NMR (400 MHz, CDCl₃, δ, ppm): 5.29 (m, 2H, CH⚌CH), 3.76 (m, 1H, CHOH), 2.34 (t, 2H, J = 7.4 Hz, CH₂C⚌N), 2.17 (s, 3H, ⚌CCH₃), 2.02 (m, 4H, CH₂CH⚌CHCH₂), 1.95 (m, 1H, CHOH), 1.45 (m, 2H, CH₂CH₂C⚌N), 1.43 (m, 2H, CH₂CHOH), 1.29 (br.s, 16H, (CH₂)₈), 0.92 (dis.t, 3H, CH₂CH₃); ¹³C NMR (100 MHz, CDCl₃, δ, ppm): 165.2, 158.8, 133.7, 133.4, 72.3, 36.9, 35.3–21.0, 17.9, 14.3; MS (ESI): m/z = 423.5 [M+Na]⁺, Calculated = 423.3. Analysis found: C, 59.98; H, 9.01; N, 6.89%. C₂₀H₃₆N₂OSe requires C, 60.00; H, 9.04; N, 6.99%.

3.4.4

3.4.4 2-[(8′R, 11′Z)-8′-Hydroxy-octadec-11′-enyl)]-5-methyl-1,3,4-selenadiazoles 3(d)

Yellow oily liquid; Yield: 62%; IR (KBr, cm⁻¹): 2929 (C—H asymm.), 2857 (C—H symm.), 1453 (C⚌N), 1159–818 (C—C aliphatic), 1262 (N—N stretch), 1075 (C—N stretch); ¹H NMR (400 MHz, CDCl₃, δ, ppm): 5.37 (m, 2H, CH⚌CH), 3.77 (m, 1H, CHOH), 2.33 (t, 2H, J = 7.6 Hz, CH₂C⚌N), 2.14 (s, 3H, ⚌CCH₃), 2.03 (m, 4H, CH₂CH⚌CHCH₂), 1.93 (m, 1H, CHOH), 1.47 (m, 2H, CH₂CH₂C⚌N) 1.45 (m, 2H, CH₂CHOH), 1.28 (br.s, 16H, (CH₂)₈), 0.91 (dis.t, 3H, CH₂CH₃); ¹³C NMR (100 MHz, CDCl₃, δ, ppm): 166.9, 159.8, 132.7, 132.3, 73.4, 36.4, 34.9–21.2, 18.8, 14.4; MS (ESI): m/z = 423.4 [M+Na]⁺, Calculated = 423.3. Analysis found: C, 59.97; H, 8.99; N, 6.94%. C₂₀H₃₆N₂OSe requires C, 60.00; H, 9.04; N, 6.99%.

4 Conclusion

Different 2,5-disubstituted-1,3,4-selenadiazoles have been synthesized from the substituted fatty acid hydrazides (1,2-dicarbonyl compound) by the reaction with acetyl chloride and Woollin’s reagent, through an intermediate product. This method is very simple, efficient and fast. The hetero cyclic selenium fatty acid derivatives have been synthesized for the first time in appreciable yield. In, recent year, attention has increasing been given to the fatty acid organo selenium compounds. The synthesis of fatty chain substituted 1,3,4-delenadiazoles, provides a systematic and general route to the synthesis of other heterocyclic compounds (containing selenium metal atom as hetero atom), for future development in the field of heterocyclic chemistry and lipid chemistry.

Acknowledgments

The authors are thankful to the Chairman, Department of Chemistry, Aligarh Muslim University, Aligarh, for providing the necessary research facility. The authors HV and AA are also thankful to the DST and CSIR, New Delhi for the award of senior research fellowship (SRF) and senior research fellowship (SRF), respectively. The authors are thankful to the SAIF, Punjab University, Chandigarh for providing spectra analyzing facilities. In part, research is also supported by FIST and UGC-SAP (DRS-I).

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Cohen V.I., . A facile synthesis of 3,5-diaryl and 3,5-dihetero aryl-1,2,4-selenadiazoles. Synthesis. 1978;1978:768-770.
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Dotsenko V.V., Frolov K.A., Krivokolysko S.G., . Synthesis of functionally substituted 1,2,4-selenadiazoles. Chem. Heterocycl. Compd.. 2013;49:353-355.
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El Sadek M.M., El-Dayem N.S.A., Hassan S.Y., Yacout G.A., . 1,3,4-Oxadiazole and selenadiazole derivatives as new C-glycosyl analogs with MAO-B, antibacterial and antifungal activities. IRJM. 2013;4:204-219.
[Google Scholar]
Farag A.M., Kandeel Z.E., M K., . A facile, one-pot synthesis of novel 2,2′-bi-(4,5-dihydro-1,3,4-selenadiazole) derivatives via dihydrazonoyl dihalides. Phosphorus Sulfur Silicon Relat. Elem.. 1994;91:129-136.
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Gunstone F.D., . Fatty acids, Part-II. The nature of the oxygenated acid present in Vernonia anthelmintica (Wild.) seed oil. J. Chem. Soc. 1954:1611-1616.
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Hope E.G., Levason W., . Recent developments in the coordination chemistry of selenoether and telluroether ligands. Coord. Chem. Rev.. 1993;122:109-170.
[Google Scholar]
Hua G., Li Y., Fuller A.L., Slawin A.M.Z., Woollins J.D., . Facile synthesis and structure of novel 2,5-disubstituted 1,3,4-selenadiazoles. Eur. J. Org. Chem. 2009:1612-1618.
[Google Scholar]
Hua G., Salwin A.M.Z., Randall A.M., Cordes B.D., Crawford L., Buhl M., Woollins J.D., . An efficient route for synthesis of phosphorus-selenium macroheterocycles. Chem. Commun.. 2013;46:2619-2621.
[Google Scholar]
Jalilian A.R., Sattari S., Bineshmarvasti M., Daneshtalab M., Shafiee A., . Synthesis and in vitro antifungal and cytotoxicity evaluation of substituted 4,5-dihydronaphtho[1,2-d][1,2,3]thia(or selena)diazoles. Farmaco. 2003;58:63-68.
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Khanna P.K., Gorte R.M., Gokhale R., . Synthesis of CdSe from cyclohepteno-1,2,3-selenadiazole and cadmium salts in ethylene glycol. Mater. Lett.. 2004;58:966-969.
[Google Scholar]
Löwig C.J., . Pogg. Ann.. 1836;37:552.
Mlochowski J., Kloc K., Lisiak R., Potaczek P., Wojtowiez H., . Developments in the chemistry of selenaheterocyclic compounds of practical importance in synthesis and medicinal biology. Arkivoc. 2007;vi:14-46.
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Mugesh G., Singh H.B., . Synthetic organo selenium compounds as antioxidants: glutathione peroxidase activity. Chem. Soc. Rev.. 2000;29:347-357.
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Ostrowski J.C., Susumu K., Robinson M.R., Therien M.J., Bazan G.C., . Near-infrared electroluminescent light-emitting devices based on ethyne-bridged porphyrin fluorophores. Adv. Mater. (Weinheim, Ger.). 2003;15:1296-1300.
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Padmavathi V., Mahesh K., Mohan A.V.N., Padmaja A., . Synthesis and bioassay of oxazolyl/thiazolyl selenadiazoles, thiadiazoles and diazaphospholes. Chem. Pharm. Bull. (Tokyo). 2009;57:561-566.
[Google Scholar]
Parveen M., Mehdi S.S., Ghalib R.M., Alam M., Hasim R., Sulaiman O., . Synthesis, characterization and antimicrobial activity of Friedelin [2,3-d] selenadiazole. Indo. J. Chem.. 2009;9:285-288.
[Google Scholar]
Patai, S., Rappoport, Z. (Eds.), 1986, 1987. The Chemistry of Organic Selenium and Tellurium Compounds, Wiley, Chichester, vol. 1, vol. 2, pp. 331, 91.
Paulmier C., . Selenium Reagents and Intermediates in Organic Synthesis. Oxford: Pergamon Press; 1986. vol. xiii, pp. 468 S
Plano D., Moreno E., Font M., Encío I., Palop J.A., Sanmartín C., . Synthesis and in vitro anticancer activities of some selenadiazole derivatives. Arch. Pharm. (Weinheim). 2010;343:680-691.
[Google Scholar]
Prabakaran K., Khan F.R.N., Jin J.S., Jeong E.D., Manivel P., . Facile synthesis of 3-aryl-1-((4-aryl-1,2,3-selenadiazol-5-yl)-sulfanyl)isoquinolines. Chem. Pap.. 2011;65 893-889
[Google Scholar]
Rauf A., Sharma S., Gangal S., . Microwave assisted one-pot synthesis of 3,5,6-trisubstituted-1,2,4-triazines from fatty acid hydrazides under solvent-free conditions and their antimicrobial activity. Arkivoc. 2007;xvi:137-147.
[Google Scholar]
Rong Z.H.A.O.H., Sen Y.U.Q., . A facile synthesis of 3,5-diaryl 1,2,4-selenadiazoles from aryl selenoamides. Chin. Chem. Lett.. 2002;13:729-730.
[Google Scholar]
Saeed M.T., Rauf A., Pasha M.K., Osman S.M., . Synthesis of 4,5-disubstituted 1,2,3-selenadiazoles from semicarbazone derivatives of long chain oxo compounds. J. Oil Tech. Assn. (India). 1991;23:60-61.
[Google Scholar]
Saravanan S., Athimoolam S., Muthusubramanian S., . Synthesis and characterization of 3-aryl-3-[4-aryl-1,2,3-selenadiazol-5-yl]-2-phenyl-2-propenenitrile. Arkivoc. 2007;i:22-32.
[Google Scholar]
Shealy Y.F., Clayton J.D., . 1,2,5-Selenadiazoles. Synthesis and properties. J. Hetero. Chem.. 1967;4:96-101.
[Google Scholar]
Shinde A.D., Sonar S.S., Shingate B.B., Shingare M.S., . Synthesis and biological screening of novel thiadiazoles, selenadiazoles and spirocyclic benzopyran by ultrasonic and microwave irradiation. Phosphorus Sulfur Silicon Relat. Elem.. 2010;185:1594-1603.
[Google Scholar]
Velusamy M., Thomas K.R.J., Lin J.T., Wen Y.S., . Benzo[1,2,5]selenadiazole bridged amines: electro-optical properties. Tetrahedron Lett.. 2005;46:7647-7651.
[Google Scholar]
Wirth T., . Chiral selenium compounds in organic synthesis. Tetrahedron. 1999;55:1-28.
[Google Scholar]
Yamashita S., Morio Y., Sasaki H., . Jpn. Kokai Tokyo Koho JP, 0545, 772[9345, 772] (C1.GO3C1/09) Chem. Abs.. 1994;120:231749p.
[Google Scholar]
Yang R., Tian R., Yan J., Zhang Y., Yang J., Hou Q., Yang W., Zhang C., Cao Y., . Deep-red electroluminescent polymers: synthesis and characterization of new low band-gap conjugated copolymers for light-emitting diodes and photovoltaic devices. Macromolecules. 2005;38:244-253.
[Google Scholar]
Zhan P., Liu X., Fang Z., Pannecouque C., Clercq D.E., . 1,2,3-Selenadiazole thioacetanilides: synthesis and anti-HIV activity evaluation. Bioorg. Med. Chem.. 2009;17:6374-6379.
[Google Scholar]

Introduction

Results and discussion

Experimental

Physical measurements
General procedure for the synthesis of fatty acid hydrazides 1(a–d)
General procedure for the synthesis of dialkyl hydrazines/substituted fatty acid hydrazides 2(a–d)
General procedure for the synthesis of 2,5-disubstituted-1,3,4-selenadiazoles 3(a–d)

Conclusion

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[Google Scholar]

[13] Farag A.M., Kandeel Z.E., M K., . A facile, one-pot synthesis of novel 2,2′-bi-(4,5-dihydro-1,3,4-selenadiazole) derivatives via dihydrazonoyl dihalides. Phosphorus Sulfur Silicon Relat. Elem.. 1994;91:129-136.
[Google Scholar]

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[Google Scholar]

[15] Hope E.G., Levason W., . Recent developments in the coordination chemistry of selenoether and telluroether ligands. Coord. Chem. Rev.. 1993;122:109-170.
[Google Scholar]

[16] Hua G., Li Y., Fuller A.L., Slawin A.M.Z., Woollins J.D., . Facile synthesis and structure of novel 2,5-disubstituted 1,3,4-selenadiazoles. Eur. J. Org. Chem. 2009:1612-1618.
[Google Scholar]

[17] Hua G., Salwin A.M.Z., Randall A.M., Cordes B.D., Crawford L., Buhl M., Woollins J.D., . An efficient route for synthesis of phosphorus-selenium macroheterocycles. Chem. Commun.. 2013;46:2619-2621.
[Google Scholar]

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[Google Scholar]

[19] Khanna P.K., Gorte R.M., Gokhale R., . Synthesis of CdSe from cyclohepteno-1,2,3-selenadiazole and cadmium salts in ethylene glycol. Mater. Lett.. 2004;58:966-969.
[Google Scholar]

[20] Löwig C.J., . Pogg. Ann.. 1836;37:552.

[21] Mlochowski J., Kloc K., Lisiak R., Potaczek P., Wojtowiez H., . Developments in the chemistry of selenaheterocyclic compounds of practical importance in synthesis and medicinal biology. Arkivoc. 2007;vi:14-46.
[Google Scholar]

[22] Mugesh G., Singh H.B., . Synthetic organo selenium compounds as antioxidants: glutathione peroxidase activity. Chem. Soc. Rev.. 2000;29:347-357.
[Google Scholar]

[23] Ostrowski J.C., Susumu K., Robinson M.R., Therien M.J., Bazan G.C., . Near-infrared electroluminescent light-emitting devices based on ethyne-bridged porphyrin fluorophores. Adv. Mater. (Weinheim, Ger.). 2003;15:1296-1300.
[Google Scholar]

[24] Padmavathi V., Mahesh K., Mohan A.V.N., Padmaja A., . Synthesis and bioassay of oxazolyl/thiazolyl selenadiazoles, thiadiazoles and diazaphospholes. Chem. Pharm. Bull. (Tokyo). 2009;57:561-566.
[Google Scholar]

[25] Parveen M., Mehdi S.S., Ghalib R.M., Alam M., Hasim R., Sulaiman O., . Synthesis, characterization and antimicrobial activity of Friedelin [2,3-d] selenadiazole. Indo. J. Chem.. 2009;9:285-288.
[Google Scholar]

[26] Patai, S., Rappoport, Z. (Eds.), 1986, 1987. The Chemistry of Organic Selenium and Tellurium Compounds, Wiley, Chichester, vol. 1, vol. 2, pp. 331, 91.

[27] Paulmier C., . Selenium Reagents and Intermediates in Organic Synthesis. Oxford: Pergamon Press; 1986. vol. xiii, pp. 468 S

[28] Plano D., Moreno E., Font M., Encío I., Palop J.A., Sanmartín C., . Synthesis and in vitro anticancer activities of some selenadiazole derivatives. Arch. Pharm. (Weinheim). 2010;343:680-691.
[Google Scholar]

[29] Prabakaran K., Khan F.R.N., Jin J.S., Jeong E.D., Manivel P., . Facile synthesis of 3-aryl-1-((4-aryl-1,2,3-selenadiazol-5-yl)-sulfanyl)isoquinolines. Chem. Pap.. 2011;65 893-889
[Google Scholar]

[30] Rauf A., Sharma S., Gangal S., . Microwave assisted one-pot synthesis of 3,5,6-trisubstituted-1,2,4-triazines from fatty acid hydrazides under solvent-free conditions and their antimicrobial activity. Arkivoc. 2007;xvi:137-147.
[Google Scholar]

[31] Rong Z.H.A.O.H., Sen Y.U.Q., . A facile synthesis of 3,5-diaryl 1,2,4-selenadiazoles from aryl selenoamides. Chin. Chem. Lett.. 2002;13:729-730.
[Google Scholar]

[32] Saeed M.T., Rauf A., Pasha M.K., Osman S.M., . Synthesis of 4,5-disubstituted 1,2,3-selenadiazoles from semicarbazone derivatives of long chain oxo compounds. J. Oil Tech. Assn. (India). 1991;23:60-61.
[Google Scholar]

[33] Saravanan S., Athimoolam S., Muthusubramanian S., . Synthesis and characterization of 3-aryl-3-[4-aryl-1,2,3-selenadiazol-5-yl]-2-phenyl-2-propenenitrile. Arkivoc. 2007;i:22-32.
[Google Scholar]

[34] Shealy Y.F., Clayton J.D., . 1,2,5-Selenadiazoles. Synthesis and properties. J. Hetero. Chem.. 1967;4:96-101.
[Google Scholar]

[35] Shinde A.D., Sonar S.S., Shingate B.B., Shingare M.S., . Synthesis and biological screening of novel thiadiazoles, selenadiazoles and spirocyclic benzopyran by ultrasonic and microwave irradiation. Phosphorus Sulfur Silicon Relat. Elem.. 2010;185:1594-1603.
[Google Scholar]

[36] Velusamy M., Thomas K.R.J., Lin J.T., Wen Y.S., . Benzo[1,2,5]selenadiazole bridged amines: electro-optical properties. Tetrahedron Lett.. 2005;46:7647-7651.
[Google Scholar]

[37] Wirth T., . Chiral selenium compounds in organic synthesis. Tetrahedron. 1999;55:1-28.
[Google Scholar]

[38] Yamashita S., Morio Y., Sasaki H., . Jpn. Kokai Tokyo Koho JP, 0545, 772[9345, 772] (C1.GO3C1/09) Chem. Abs.. 1994;120:231749p.
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[39] Yang R., Tian R., Yan J., Zhang Y., Yang J., Hou Q., Yang W., Zhang C., Cao Y., . Deep-red electroluminescent polymers: synthesis and characterization of new low band-gap conjugated copolymers for light-emitting diodes and photovoltaic devices. Macromolecules. 2005;38:244-253.
[Google Scholar]

[40] Zhan P., Liu X., Fang Z., Pannecouque C., Clercq D.E., . 1,2,3-Selenadiazole thioacetanilides: synthesis and anti-HIV activity evaluation. Bioorg. Med. Chem.. 2009;17:6374-6379.
[Google Scholar]

Synthesis of novel 2,5-disubstituted-1,3,4-selenadiazoles from fatty acid hydrazides

Abstract

Keywords

Hydrazine

Woollin’s reagent

Selenadiazole

Fatty acid hydrazide

1 Introduction

2 Results and discussion

3 Experimental

3.1 Physical measurements

3.2 General procedure for the synthesis of fatty acid hydrazides 1(a–d)

3.3 General procedure for the synthesis of dialkyl hydrazines/substituted fatty acid hydrazides 2(a–d)

3.3.1 N′-Acetyl undec-10-enoic hydrazide 2(a)

3.3.2 N′-Acetyl-(9Z)-octadec-9-enoic hydrazide 2(b)

3.3.3 N′-Acetyl-(9Z, 12R)-12-hydroxy-octadec-9-enoic hydrazide 2(c)

3.3.4 N′-Acetyl-(9R, 12Z)-9-hydroxy-octadec-12-enoic hydrazide 2(d)

3.4 General procedure for the synthesis of 2,5-disubstituted-1,3,4-selenadiazoles 3(a–d)

3.4.1 2-(Dec-9′-enyl)-5-methyl-1,3,4-selenadiazoles 3(a)

3.4.2 2-[(8′Z)-Heptadec-8′-enyl]-5-methyl-1,3,4-selenadiazoles 3(b)

3.4.3 2-[(8′Z, 11′R)-11′-Hydroxy-octadec-8′-enyl)]-5-methyl-1,3,4-selenadiazoles 3(c)

3.4.4 2-[(8′R, 11′Z)-8′-Hydroxy-octadec-11′-enyl)]-5-methyl-1,3,4-selenadiazoles 3(d)

4 Conclusion

Acknowledgments

References

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