Nmr spectra of some n-(tetra-o-acetyl-dglycopyranosyl) thiosemicarbazones from natural carbonyl compounds - Nguyen Dinh Thanh

134 Tạp chí phân tích Hóa, Lý và Sinh học - Tập 20, Số 2/2015 NMR SPECTRA OF SOME N-(TETRA-O-ACETYL--D- GLYCOPYRANOSYL)THIOSEMICARBAZONES FROM NATURAL CARBONYL COMPOUNDS Đến tòa soạn 19 – 8 – 2014 Nguyen Dinh Thanh, Truong Thi Thu, Ngo Thi Bich Dao Faculty of Chemistry, VNU University of Science (Vietnam National University, Ha Noi), 19 Le Thanh Tong, Hanoi; Hoang Thi Kim Van Viet Tri University of Industry (Phu Tho) SUMMARY PHỔ NMR CỦA MỘT SỐ N-(TETRA-O-ACETYL--D- GLYCOPYRANOSYL)THIOSEMICARBAZON TỪ CÁC HỢP CHẤT CARBONYL THIÊN NHIÊN Các N-(tetra-O-acetyl--D-glycopyranosyl)thiosemicarbazon của một số aldehyd và keton có nguồn gốc thiên nhiên đ được tổng hợp và nghiên cứu phổ MNMR. Phổ 1H và 13 C NMR của các thiosemicarbazon này đ được thảo luận. Các tín hiệu cộng hưởng từ trong phổ NMR của chúng chỉ ra mối quan hệ giữa cấu trúc và vị trí của tín hiệu cộng hưởng. Cấu hình  của các thiosemicarbazon này được xác nhận dựa vào hằng số ghép cặp J = 9.5–8.5 Hz giữa proton NH-4 của liên kết thiosemicarbazon và proton H-1‟ trong hợp phần đư ng. 1. INTRODUCTION Carbonyl compounds in nature is a source of precious aromas, some of them are more notable active, such as antibacterial, antifungal, anticancer In addition, it also has many applications in the food industry as flavoring for confectionery, perfumes. Studies on the synthesis of thiosemicarbazones from natural carbonyl compounds have not 135 been studied much, only very few of the references mentioned in this regard [1,6]. In order to contribute to the research in the field of chemistry of monosaccharides, in this article, we have reported some results in synthesis and spectral study of some thiosemicarbazones containing monosaccharide component with some natural carbonyl compounds. 2. EXPERIMENTAL PART N-(Tetra-O-acetyl--D- glycopyranosyl)thiosemicarbazides were prepared by synthetic methods in [7]. N- (Tetra-O-acetyl--D- glycopyranosyl)thiosemicarbazones were synthesized in bellow procedure. Their 1 H and 13 C NMR spectra was recorded on FT-NMR Avance AV500 Spectrometer (Bruker, Germany) at 500.13 MHz and 125.76 MHz, respectively, using DMSO-d6 as solvent and TMS as an internal standard. Spectral data of 1 H and 13 C NMR were summarized in Tables 1 and 2. Aldehydes and ketones used in this article have been isolated from Vietnamese plant oils by using known common suitable methods. Cinnamaldehyde was isolated from Cinnamomum cassia (Bl.) oil. Menthone was prepared from menthol of Mentha arvensis (L.) plant. Camphor was isolated from Cinnamomum camphora (L.) Nees. et Eberm plant. General procedure tetra-O-acetyl--D- glycopyranosyl thiosemicarbazones. A mixture of corresponding N-(tetra-O- acetyl--D- glycopyranosyl)thiosemicarbazide (2 mmol), corresponding natural carbonyl compound (2 mmol), glacial acetic acid (0.5 ml) in absolute ethanol (9 ml) was heated at reflux using domestic microwave oven in 8 min at power of 800W. The solvent was evaporated to one half the original volumes. The resulting colorless crystals were filtered by suction. The crude product when recrystallized from 96% ethanol to afford the title compounds 1-5. 3. RESULTS AND DISCUSSION The 1 H and 13 C NMR spectral data of tetra-O-acetyl--D-glycopyranosyl thiosemicarbazones 1-5 from natural carbonyl compounds were listed in Table 1 and 2. The 1 H and 13 C NMR spectra of these thiosemicarbazones showed a distinct signal regions specified to each type of proton and carbon-13 atoms are present in molecule of the compounds. The structures of these thiosemicarbazones are represented below. 136 b a 6" 5" 4" 3" 2" 1" 6' 5'4' 3' 2' 1' 4 3 2 1 O OAc AcO OAc NH C S NH N R 2 R 1 1, 2 10'' 9'' 8'' 7'' 6'' 5'' 4'' 3'' 2'' 1'' 6' 5'4' 3' 2' 1' 4 3 2 1O OAc AcO OAc NH C S NH N R 2 CH3 CH3 CH3 R 1 3,4 CH3 CH3 CH3 O OAc AcO OAc NH C S NH N R 2 R 1 6' 5'4' 3' 2' 1' 4 3 2 1 5 Cinnamaldehyde peracetylated glycopyranosyl thiosemicarbazones: 1 R1=H, R2=OAc; 2 R1=OAc, R2=H Menthone peracetylated glycopyranosyl thiosemicarbazones: 3 R1=H, R2=OAc; 4 R1=OAc, R2=H Camphor peracetylated glycopyranosyl thiosemicarbazones: 5 R1=H, R2=OAc Protons in NH-2 and NH-4 bonds in thiosemicarbazone group have signal at =11.94–11.89 ppm (singlet, for cinnamaldehyde thiosemicarbazones), δ=10.86–10.50 ppm (singlet, for camphor and menthone thiosemicarbazones) and =8.55–8.336 ppm (doublet, J=9.5–9.0 Hz, for cinnamaldehyde thiosemicarbazones) and δ=8.17–8.06 ppm (doublet, J=9.5– 9.0 Hz, for camphor and menthone thiosemicarbazones), respectively. Proton of azomethin group (CH=N) shows chemical shift at =7.94–7.93 ppm (singlet), and carbon atom in this group has signal at about 146,0 ppm. Aromatic protons have resonance signals in region at =7.57–7.33 ppm (doublet, J =7.5–7.25 Hz, for cinnamaldehyde thiosemicarbazones). There are two proton signals for di- trans-substituted alkene appear at δ=7.07–6.95 ppm with the coupling constants J=16.00 Hz. These values of the coupling constants demonstrate the alkene combined with aromatic rings in cinnamaldehyde component has trans- configuration. Protons in CH3 group in acetate functions have signals in region at =2.14–1.90 ppm. Protons of monosaccharide component have signals including in range from 5.97 ppm to 3.98 ppm. The distinct structure pattern of galactopyranose ring, compared with the one of glucopyranose ring, is confirmed by coupling constant between H-4” and H-3” protons with 3J=3.25– 3.00 Hz in galactopyranose ring, compared with the coupling constant 3 J=9.75–9.25 Hz in glucopyranose ring. Protons on C-1’ and C-2’ carbon atoms in glucose and galactose ring have coupling interaction with the constants 3 J=9.5–8.5 Hz, in relation to H–H interaction of trans type, therefore, thiosemicarbazide linkage group is equatorial direction, i.e. all tetra-O- acetyl--D-glycopyranosyl thiosemicarbazones have -anomeric configuration [4]. The 1 H NMR spectrum of camphor N- (tetra-O-acetyl--D- glucopyranosyl)thiosemicarbazone, for 137 instance, shows the proton resonance signals present in the camphor component, located in the region δ=1.05–0.67 ppm, while proton resonance signals in NH-2 (δ= 10.50 ppm) shifted dramatically toward a down-field due to the anisotropic effect of the >C=S and >C=N– adjacent links, whereas the position of the proton resonance signals of NH-4 (δ=8.17ppm) only changed a little and appears as doublet at δ=8.17 ppm with the constant pairing pair 3 J=9.00 Hz. The long-range interactions between carbon atoms and protons in the HMBC spectrum of menthone 4-(2,3,4,6-tetra- O-acetyl--D- glucopyranosyl)thiosemicarbazone can be described as follows: Table 1. 1 H NMR Spectra data of tetra-O-acetyl--D- glycopyranosyl)thiosemicarbazones [ (ppm), multicity, J (Hz)] Proton Cinnamaldehyde thiosemicarbazones Menthone thiosemicarbazones Camphor thiosemicarbazo nes 1 2 3 4 5 NH-2 11.89(s,1H) 11.94(s,1H) 10.85(s,1H) 10.86(s,1H) 10.50(s,1H) NH-4 8.55(d,1H,J9.0) 8.33(d,1H,J9.50) 8.07 (d,1H,J9.5) 8.07 (d,1H,J9.50) 8.17(d,1H,J9.0) CH=N 7.93(d,1H,J9.0) 7.94(d,1H,J9.00) - - - CHa 6.90(dd,1H,J16.0) 6.94 (dd,1H,J16.0) - - - CHb 7.07 (d,1H,J9.5,16.0) 7.07(d,1H,J16.0) - - - H-1’ 5.97(t,1H,J9.0) 5.92(t,1H,J9.50) 5.84 (t,1H,J8.75) 5.84 (t,1H,J9.25) 5.80(t,1H,J9.25) H-2’ 5.22(t,1H,J9.25) 5.20(t,1H,J9.50) 5.04 (t,1H,J9.5) 5.04 (t,1H,J9.50) 5.11(t,1H,J9.25) H-3’ 5.40(t,1H,J9.5) 5.39 (dd,1H,J3.25) 5.42 (t,1H,J9.25) 5.42 (t,1H,J9.50) 5.42(t,1H,J9.5) H-4’ 4.95(t,1H,J9.5) 5.19(d,1H,J3.00) 4.94 (t,1H,J9.75) 4.95 (t,1H,J9.50) 4.96(m,1H) H-5’ 4.06(ddd,1H,J2.0, 4.5,9.5) 4.04-4.03(m,2H) 4.04- 4,03(m,1H) 4.07- 4.02(m,1H) 4.34(d,1H,J9.25) H-6’a 4.19(dd,1H,J4.5, 12.5) 4.32-4.34(m,1H) 4.16(dd,1H, J4.75,12.5) 4.16(dd,1H,J5. 00,12.50) 4.20(dd,1H,J4.5, 12.75) H-6’b 3.98(d,1H,J11.5) 4.04-4.03(m,2H) 3.98(d,1H, J2.0,12.5) 3.98(dd,1H, J2.00,12.25) 4.01 (d,1H,J2.5,12.25) H-2” 7.57(d,2H,J7.5) 7.59(d,2H,J7.50) (A) 3,37- 0,86(m, 16H) (B) 2,92- 0,86(16H) (C) 1,05- 0,67(m,16H) H-3” 7.40(t,2H,J7.25) 7.40(d,2H,J7.50) 138 Proton Cinnamaldehyde thiosemicarbazones Menthone thiosemicarbazones Camphor thiosemicarbazo nes 1 2 3 4 5 H-4” 7.33(t,1H,J7.5) 7.33(t,1H,J7.25) 2,23-2,19 (m, 1H) 1,78-1,76 (m, 1H) 1,67-1,63 (m, 1H) 1,18-1,14 (m, 4H) 0,94-0,86 (m, 9H) 2,23-2,19 (m, 1H) 1,78-1,76 (m, 1H) 1,67-1,63 (m, 1H) 1,18-1,14 (m, 4H) 0,94-0,86 (m, 9H) 0,81(s,1H) 0,76(s,2H) 1,00(s,3H) 0,89(s, 6H) 0,71-0,67(m,4H) H-5” 7.40(t,2H,J7.25) 7.40(d,2H,J7.50) H-6” 7.57(d,2H,J7.5) 7.59(d,2H,J7.50) CH3CO 2.00-1.93(s,12H) 2.14-1.94(s,12H) 1.99-1.92 1.95- 1.90(s,12H) 2.01-1.95 Note: (A), (B), (C): proton signals in methone and camphor, respectively. Table 2. 13 C NMR Spectra data of N-(tetra-O-acetyl--D- glycopyranosyl)thiosemicarbazones Proton Cinnamaldehyde thiosemicarbazones Menthone thiosemicarbazones Camphor thiosemicarbazones 1 2 3 4 5 C=S 177.9 177.9 179.1 179.1 178.6 COCH3 170.0- 169.3 170.0- 169.3 170.0- 169.3 170.0- 169.3 170.0-169.3 C-1’ 81.3 81.3 80.8 80.8 81.0 C-2’ 70.8 70.8 70.5 70.5 70.4 C-3’ 72.7 72.7 72.3 72.3 72.3 C-4’ 67.9 67.9 68.2 68.2 68.2 C-5’ 72.3 72.3 72.1 72.1 72.1 C-6’ 61.8 61.8 61.8 61.8 61.7 CHa 124.7 124.7 - - - CHb 135.7 135.7 - - - C-1” 140.0 140.0 160.3 160.3 168.7 C-2” 129.0 129.0 50.2 50.2 52.7 C-3” 128.9 128.9 27.8 27.8 34.8 C-4” 127.0 127.0 32.5 32.5 32.1 C-5” 128.9 128.9 33.4 33.4 47.3 139 Proton Cinnamaldehyde thiosemicarbazones Menthone thiosemicarbazones Camphor thiosemicarbazones 1 2 3 4 5 C-6” 129.0 129.0 35.4 35.4 47.6 CH3CO 20.5-20.3 20.5-20.3 20.5-20.2 20.5-20.2 20.5-20.2 -CH=N- 146.0 146.0 - - - CH(CH3)2 - - 26.3; 21.7; 19.0 25.8; 21.7; 19.0 26.7; 18.9; 10.8 CH3 - - 21.2 21.2 18.4 O H O H H H H N O O C O C N S H N H O CH3 O CH3 CH3 O CH3 O H H CH3 CH3 CH3 140 4. 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