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ĐẠI HỌC QUỐC GIA HÀ NỘI TRƢỜNG ĐẠI HỌC KHOA HỌC TƢ̣ NHIÊN Chu Thị Thuý Hằng NGHIÊN CỨU TỔNG HỢP MỘT SỐ PERACETYL--D-GLUCOPYRANOSYL THIOSEMICARBAZON CỦA 4-ACETYLSYDNONE THẾ Chun ngành: Hố Hữu Mã sớ: 60 44 27 LUẬN VĂN THẠC SĨ KHOA HỌC Hà Nội – 2011 TIEU LUAN MOI download : skknchat@gmail.com ĐẠI HỌC QUỐC GIA HÀ NỘI TRƢỜNG ĐẠI HỌC KHOA HỌC TƢ̣ NHIÊN Chu Thị Thuý Hằng NGHIÊN CỨU TỔNG HỢP MỘT SỐ PERACETYL--D-GLUCOPYRANOSYL THIOSEMICARBAZON CỦA 4-ACETYLSYDNONE THẾ Chun ngành: Hố Hữu Mã sớ: 60 44 27 LUẬN VĂN THẠC SĨ KHOA HỌC NGƢỜI HƢỚNG DẪN KHOA HỌC : PGS TS Nguyễn Đình Thành Hà Nội – 2011 TIEU LUAN MOI download : skknchat@gmail.com MỤC LỤC LỜI CẢM ƠN MỤC LỤC i CÁC KÝ HIỆU VIẾT TẮT vi DANH MỤC CÁC BẢNG vii DANH MỤC CÁC HÌNH VÀ SƠ ĐỒ viii MỞ ĐẦU Chương TỔNG QUAN 1.1 TỔNG QUAN VỀ SYDNONE 1.1.1 Cấu trúc sydnone 1.1.2 Tính chất sydnone 1.1.2.1 Độ bền sydnone 1.1.2.2.Tính chất hóa học sydnone 1.1.3 Các phương pháp tổng hợp sydnone 11 1.2 TỔNG QUAN VỀ GLYCOSYL ISOTHIOCYANAT 13 1.2.1 Giới thiệu glucosyl isothiocyanat 13 1.2.2 Phương pháp tổng hợp glycosyl isocyanat glucosyl isothiocyanat 13 1.2.3 Tính chất hoá học glycosyl isocyanat glycosyl isothiocyanat 15 1.1.3.1 Phản ứng với amoniac amin 15 1.2.3.2 Phản ứng với aminoacid 16 1.2.3.3 Phản ứng với amid 16 1.2.3.4 Phản ứng với aminoaceton hydrocloride 17 1.2.3.5.Phản ứng với 2-cloroethylamin hydrocloride 17 1.2.3.6 Phản ứng với diamin diazomethan 18 i TIEU LUAN MOI download : skknchat@gmail.com 1.3 TỔNG QUAN VỀ THIOSEMICARBAZID 18 1.3.1 Tổng hợp thiosemicarbazid 18 1.3.1.1 Phản ứng isothiocyanat hydrazin 19 1.3.1.2 Phản ứng khử thiosemicarbazon NaBH4 19 1.3.1.3 Phản ứng hydrazin với dẫn xuất acid thiocarbamic 19 1.3.1.4 Phản ứng cyanohydrazin với hydrosulfide 20 1.3.1.5 Phản ứng tổng hợp dẫn xuất di- trithiosemicarbazid từ amin 20 1.3.2 Tính chất thiosemicarbazid 20 1.3.2.1 Phản ứng với aldehyd 20 1.3.2.2 Phản ứng đóng vịng thiosemicarbazid tạo thành thiadiazole 20 1.4 TỔNG QUAN VỀ THIOSEMICARBAZON 22 1.5 SỬ DỤNG LÒ VI SĨNG TRONG HỐ HỌC CARBOHYDRATE 23 Chương THỰC NGHIỆM 27 2.1 TỔNG HỢP CÁC HỢP CHẤT 4-acetyl-3-arylsydnone 29 2.1.1 Tổng hợp chất 3-arylsydnone 29 2.1.1.1 Tổng hợp 3-phenylsydnone (4a) 29 2.1.1.2 Tổng hợp 3-(4-fluorophenyl)sydnone (4b) 31 2.1.1.3 Tổng hợp 3-(4-methylphenyl)sydnone (4c) 32 2.1.1.4 Tổng hợp 3-(4-clorophenyl)sydnone (4d) 34 2.1.1.5 Tổng hợp 3-(4-ethoxyphenyl)sydnone (4e) 35 2.1.1.6 Tổng hợp 3-(4-carboxyphenyl)sydnone (4f) 37 2.1.1.7 Tổng hợp 3-(3,4-diclorophenylphenyl)sydnone (4g) 39 2.1.1.8 Tổng hợp 3-(3,5-diclorophenyl)sydnone (4h) 41 2.1.1.9 Tổng hợp 3-(5-cloro-2-methylphenyl)sydnone (4i) 42 2.1.2 Tổng hợp 4-acetyl-3-arylsydnone 44 ii TIEU LUAN MOI download : skknchat@gmail.com 2.1.2.1 Tổng hợp 4-acetyl-3-phenylsydnone (5a) 44 2.1.2.2.Tổng hợp 4-acetyl-3-(4-fluorophenyl)sydnone (5b) 45 2.1.2.3.Tổng hợp 4-acetyl-3-(4-methylphenyl)sydnone (5c) 45 2.1.2.4 Tổng hợp 4-acetyl-3-(4-clorophenyl)sydnone (5d) 46 2.1.2.5 Tổng hợp 4-acetyl-3-(4-ethoxyphenyl)sydnone (5e) 46 2.1.2.6 Tổng hợp 4-acetyl-3-(4-carboxyphenyl)sydnone (5f) 47 2.1.2.7 Tổng hợp 4-acetyl-3-(3,4-diclorophenyl)sydnone (5g) 47 2.1.2.8 Tổng hợp 4-acetyl-3-(3,5-diclorophenyl)sydnone (5h) 48 2.1.2.9 Tổng hợp 4-acetyl-3-(5-cloro-2-methylphenyl)sydnone (5i) 48 2.2 TỔNG HỢP TETRA-O-ACETYL-β-D-GLUCOPYRANOSYL THIOSEMICARBAZID 49 2.2.1 Tổng hợp tetra-O-acetyl-α-D-glucopyranosyl bromide 49 2.2.2 Tổng hợp tetra-O-acetyl--D-glucopyranosyl isothiocyanat 50 2.2.3 Tổng hợp tetra-O-acetyl--D-glucopyranosyl thiosemicarbazid 50 2.3 TỔNG HỢP CÁC HỢP CHẤT 4-acetyl-3-arylsydnone (TETRA-O-ACETYL- β-DGLUCOPYRANOSYL) THIOSEMICARBAZON 51 2.3.1 Tổng hợp 4-acetyl-3-phenylsydnone (tetra-O-acetyl-β-D-glucopyranosyl)thiosemicarbazon (8a) 51 2.3.2 Tổng hợp 4-acetyl-3-(4-fluorophenyl)sydnone (tetra-O-acetyl-β-Dglucopyranosyl)thiosemicarbazon (8b) 52 2.3.3 Tổng hợp 4-acetyl-3-(4-methylphenyl)sydnone (tetra-O-acetyl-β-Dglucopyranosyl)thiosemicarbazon (8c) 52 2.3.4 Tổng hợp 4-acetyl-3-(4-clorophenyl)sydnone (tetra-O-acetyl-β-Dglucopyranosyl)thiosemicarbazon (8d) 53 2.3.5 Tổng hợp 4-acetyl-3-(4-ethoxyphenyl)sydnone (tetra-O-acetyl-β-Dglucopyranosyl)thiosemicarbazon (8e) 53 iii TIEU LUAN MOI download : skknchat@gmail.com 2.3.6 Tổng hợp 4-acetyl-3-(4-carboxyphenyl)sydnone (tetra-O-acetyl-β-Dglucopyranosyl)thiosemicarbazon (8f) 54 2.3.7 Tổng hợp 4-acetyl-3-(3,4-diclorophenyl)sydnone (tetra-O-acetyl-β-Dglucopyranosyl)thiosemicarbazon (8g) 54 2.3.8 Tổng hợp 4-acetyl-3-(3,5-diclorophenyl)sydnone (tetra-O-acetyl-β-Dglucopyranosyl)thiosemicarbazon (8h) 54 2.3.9 Tổng hợp 4-acetyl-3-(5-cloro-2-methylphenyl)sydnone (tetra-O-acetyl-β-Dglucopyranosyl)thiosemicarbazon (8i) 55 Chương KẾT QUẢ VÀ THẢO LUẬN 56 3.1 VỀ TỔNG HỢP 4-ACETYL-3-ARYLSYDNONE 56 3.1.1 Tổng hợp hợp chất N-arylglycine (2a-i) 56 3.1.2 Tổng hợp hợp chất N-nitroso-N-arylglycine (3a-i) 60 3.1.3 Tổng hợp hợp chất 3-arylsydnone (4a-i) 62 3.1.4 Tổng hợp 4-acetyl-3-arylsydnone (5a-i) 64 3.1.4.1 Tổng hợp 4-acetyl-3-arylsydnone 64 3.1.4.2 Dữ kiện phổ 4-acetyl-3-arylsydnone 66 3.2 VỀ TỔNG HỢP TETRA-O-ACETYL-β-D-GLUCOPYRANOSYL ISOTHIOCYANAT 68 3.3 VỀ TỔNG HỢP TETRA-O-ACETYL-β-D-GLUCOPYRANOSYL THIOSEMICARBAZID 70 3.4 VỀ TỔNG HỢP CÁC 4-ACETYL-3-ARYLSYDNONE TETRA-O-ACETYL- β-DGLUCOPYRANOSYL THIOSEMICARBAZON 72 3.4.1 Tổng hợp (tetra-O-acetyl-β-D-glucopyranosyl)thiosemicarbazon 4-acetyl-3arylsydnone (8a-i) 72 3.4.2 Dữ kiện phổ 4-acetyl-3-arylsydnone (tetra-O-acetyl-β-D-glucopyranosyl thiosemicacbazon 73 iv TIEU LUAN MOI download : skknchat@gmail.com (LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the (LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the KẾT LUẬN 85 TÀI LIỆU THAM KHẢO 86 Tiếng Việt 86 Tiếng Anh 86 v TIEU LUAN MOI download : skknchat@gmail.com (LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the (LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the CÁC KÝ HIỆU VIẾT TẮT 13 C NMR: Phổ cộng hưởng từ hạt nhân carbon-13 (13C Nuclear Magnetic Resonance) COSY: Phổ tương quan 1H-1H (Correlated Spectroscopy) DMF: dimethyl fomamid DMSO: dimethyl sulfoxide DMSO-d6: dimethyl sulfoxide deuteri hóa H NMR: Phổ cộng hưởng từ hạt nhân proton (1H Nuclear Magnetic Resonance) HMBC: Phổ tương tác xa 13C-1H (Hetherronuclear Multiple Bond Coherence) HRMS: Phổ khối lượng phân giải cao (High Resolution Mass Spectrometry) HSQC: Phổ tương tác gần 13C-1H (Hetherronuclear Single Quantum Correlation) IR: Phổ hồng ngoại (Infrared Spectroscopy) MS: Phổ khối lượng (Mass Spectrometry) : độ chuyển dịch hóa học vi TIEU LUAN MOI download : skknchat@gmail.com (LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the Kí hiệu R m/z 8c 4-Me 423, 422, 385, 380, 341, 298, 296, 283, 140, 139, 117, 116, 102, 97, 81, 76, 74, 62, 59, 58 4-Cl 518, 517, 502, 501, 500, 486, 485, 484, 473, 465, 464, 463, 462, 460, 445, 444, 443, 430, 429, 424, 423, 422, 421, 420, 402, 370, 342, 331, 295, 283, 169, 139, 124, 117, 109, 108, 102, 81, 59 4-OEt 523, 522, 522, 518, 507, 506, 502, 501, 500, 486, 485, 484, 482, 464, 463, 462, 444, 430, 424, 423, 422, 348, 331, 295, 283, 255, 140, 139, 124, 117, 117, 109, 102, 97, 81, 76, 74, 62, 59, 58 4-COOH 519, 517, 502, 501, 500, 487, 486, 485, 484, 464, 463, 462, 460, 446, 445, 444, 430, 424, 423, 422, 413, 402, 370, 331, 295, 283, 240, 195, 181, 169, 139, 124, 117, 109, 102, 85, 81, 80, 59 3.4-diCl 523, 522, 522, 518, 517, 507, 502, 501, 500, 487, 486, 485, 484,473, 465, 464, 463, 462, 448, 444, 430, 429, 424 422, 421, 402, 342, 331, 295, 283, 169, 139, 132, 124,117,115, 109,102,59 8h 3,5-diCl 502, 501, 500, 486, 485, 484, 464, 463, 362, 460, 445, 444, 433, 431, 423, 422, 413, 378, 376, 375, 374, 370, 332, 331, 310, 309, 308, 295, 283, 267, 255, 239, 181, 139, 124, 117, 109, 81, 59 8i 2-Me-5-Cl 8d 8e 8f 8g 523, 522, 522, 518, 517, 507, 502, 501, 500, 487, 486, 485, 484,473, 465, 464, 463, 462, 448, 444, 430, 429, 424 422, 421, 402, 342, 331, 295, 283, 169, 139, 132, 124,117,115, 109,102,59 83 TIEU LUAN MOI download : skknchat@gmail.com (LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the (LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the OAc O AcO AcO OAc NH NH N OAc S C N H NH O NH NH OAc N O m/z 517 O AcO AcO S m/z 422 OAc O AcO AcO NH OAc CH3 NH N S C R N H N O O [M+H]+ OAc OAc OAc O AcO AcO AcO AcO AcO AcO OAc O NH OAc O OAc N S m/z 517 m/z 331 CH3 NH C N H O N O CH3COOH OAc OAc O AcO hay AcO AcO O +H m/z 272 OAc m/z 271 m/z 271 Hình 3.4.2.h Sự phân mảnh phổ MS hợp chất 3-aryl-4acetylsydnone (tetra-O-acetyl-β-D-glucopyranosyl)thiosemicarbazon (8a-i) 84 TIEU LUAN MOI download : skknchat@gmail.com (LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the (LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the KẾT LUẬN Đã tổng hợp hợp chất 3-arylsydnone, xuất phát từ anilin qua glycine tương ứng Từ 3-arylsydnone nhận được, điều chế hợp chất 4-acetyl-3-arylsydnone phản ứng acetyl hoá sử dụng acid acetic với có mặt P2O5 anhydrid acetic với có mặt acid percloric Đã tổng hợp hợp chất 3-aryl-4-acetylsydnone (tetra-O-acetyl-β-Dglucopyranosyl)thiosemicarbazon phản ứng tetra-O-acetyl-β-D- glucopyranosyl thiosemicarbazid 4-acetyl-3-arylsydnone tương ứng có mặt xúc tác acid acetic thực lị vi sóng Cấu trúc hợp chất 3-aryl-4-acetylsydnone (tetra-O-acetyl-β-Dglucopyranosyl)thiosemicarbazon xác nhận phương pháp vật lí đại phổ IR, phổ 1H NMR, 13C NMR kết hợp kĩ thuật phổ hai chiều (COSY, HSQC HMBC) phổ MS 85 TIEU LUAN MOI download : skknchat@gmail.com (LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the (LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the TÀI LIỆU THAM KHẢO Tiếng Việt Lê Huy Chính, Nguyễn Vũ Trung (2005), Cẩm nang vi sinh vật y học, NXB Y học, Hà Nội Nguyễn Lân Dũng, Nguyễn Đình Quyến, Nguyễn Văn Ty (2003), Vi sinh vật học, NXB Giáo dục, Hà Nội, tr 25 Phan Tống Sơn, Trần Quốc Sơn, Đặng Như Tại (1980), Cơ sở hóa học hữu cơ, NXB Đại học trung học chuyên nghiệp, Hà Nội, tr 111 Đặng Như Tại (1998), Cơ sở hóa học lập thể, NXB Giáo dục, Hà Nội, tr 24 Nguyễn Đình Thành (2011), Cơ sở phương pháp phổ ứng dụng hoá học– NXB Khoa học Kỹ thuật, Hà Nội Nguyễn Minh Thảo (2001), Tổng hợp hữu cơ, NXB Đại học Quốc Gia Hà Nội, Hà Nội Tiếng Anh Asha Budakoti, Mohammad Abid and Amir Azam, Assony S J (1961), “The chemistry of isothiocyanate”, Organic chemistry of sulfur compounds, Ed Kharasch N, Oxford, Vol 9, pp 326-327 BrowneD.L., Harrity J.P.A (2010), “Recent developments in the chemistry of sydnone”, Tetrahedron, 66, 553-568 10 Budakoti A., Abid M and Azam A (1961), “The chemistry of isothiocyanates”, Org Chem Sulf Comp., Ed Kharasch N, Oxford, 9,.326-327 11 Camarasa M J., P Fernandez-Resa, M T Garcia-Lopez, F G de las Heras, 86 TIEU LUAN MOI download : skknchat@gmail.com (LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the (LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the P P Mendez-Castrillon, and A San Felix (1984), “A New Procedure for the Synthesis of Glycosyl Isothiocyanates”, Synthesis, pp 509-510 12 Campana M., Laborie C., Barbier G., Assan R and Milcent R (1991), “Synthesis and cytotoxic activity on islets of Langerhans of benzamid thiosemicarbazon derivatives”, Eur J Med Chem., 26, 273-278 13 Castiñeiras A , E Bermejo, J Valdes-Martínez, G Espinosa-Pérez and D X West (2000),“Structural study of two N(3)-substituted thiosemicarbazid copper(II) complexes”, J Mol Struct., 522, 271-278 14 CherepanovI.A., BronovaD.D., BalantsevaE Yu., KalininV.N., (1997), “An effective synthesis of 4-alkynyl-substituted sydnone”, Mendeleev Commun., 7, 93-94 15 Dimmock, J R.; Jonnalagadda, S S.; Hussein, S.; Tewari, S.; Quail, J W.; Reid, R S.; Delbaere, L T J.; Prasad, L (1990) Evaluation of some thiosemicarbazons of arylidene ketones and analogues for anticonvulsant activities, Eur J Med Chem., 25, 581 16 Dolman, S J., Gosselin, F., O'Shea, P D., Davies, I W (2006), “Superior Reactivity of Thiosemicarbazids in the Synthesis of 2-Amino-1,3,4-oxadiazoles”, J Org Chem, 71(25), 9548-9551 17 DunkleyC S., ThomanC J., (2003), “synthesis and biological evaluation of a novel phenyl substituted sydnone series as potential antitumor agents”, Bioorg Med Chem Lett., 13, 2899-2901 18 Ferrari M.B., Capacchi S , Reffo G., Pelosi G., Tarasconi P., Albertini R.,Pinelli S and Lunghi P (2000) “Synthesis, structural characterization and biological activity of p-fluorobenzaldehyde thiosemicarbazons and of a nickel complex”, J Inorg Biochem., 81, 89-97 87 TIEU LUAN MOI download : skknchat@gmail.com (LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the (LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the 19 Fuentes J., Moreda W., Ortiz C., Robina I and Welsh C (1992), “Partially protected D-glucopyranosyl isothiocyanates Synthesis and transformations into thiourea and hetherrocyclic derivatives”, Tetrahedron, 48, Issue 31, 6413-6424 22 Hegde J.C., Girisha K.S., Adhikari A., Kalluraya B (2008), “Synthesis and antimicrobial activities of a new series of 4-S-[41-amino-51-oxo-61-substituted benzyl-41,51-dihydro-11,21,41-triazin-3-yl]mercaptoacetyl-3-arylsydnone”, Eur J Med Chem., 43, 2831-2834 23 José S Casas, María V Casto, María C Cifuentes, Juán C GarcíaMonteagudo, Agustín Sánchez, José Sordo and Ulrich Abram (2004) “Complexes of dicloro[2-(dimethylaminomethyl)phenyl-C1,N]gold(III), [Au(dampC1,N)Cl2], with formylferrocene thiosemicarbazons: synthesis, structure and cytotoxicity”, J Inorg Biochem., Vol 98, Issue 6, pp 1009–1016 24 Kalinin V.N., Lebedev S.N., Cherepanov I.A., Godovikov I.A., Lyssenko K.A., Hey-Hawkins E (2009), “4-Diphenylphosphinosydnone imines as bidentate ligands”, Polyhedron, 28, 2411-2417 25 Kavali J R., Badami B.V (2000), “1,5-Benzodiazepine derivatives of 3arylsydnone: synthesis and antimicrobial activity of 3-aryl-4-[2′-aryl-2′,4′,6′,7′tetrahydro-(1′H)-1′,5′-benzodiazepine-4′-yl]sydnone”, Il Farmaco, 55, 406-409 26 Marisa Belicchi Ferrari, Franco Bisceglie, Giorgio Pelosi, Pieralberto Tarasconi, Roberto Albertini and Silvana Pinelli (2001), “New methyl pyruvate thiosemicarbazons and their copper and zinc complexes: synthesis, characterization, X-ray structures and biological activity”, J Inorg Biochem., Vol 87, Issue 3, 1, pp 137-147 27.Mei-Hsiu Shih (2002), “Studies on the syntheses of hetherrocycles from 3arylsydnone-4-carbohydroximic acid chlorides with N-arylmaleimides, 88 TIEU LUAN MOI download : skknchat@gmail.com (LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the (LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the [1,4]naphthoquinone and aromatic amines”, Tetrahedron, 58, 10437–10445 28.Mei-Hsiu Shih, Cheng-Ling Wu (2005), “Efficient syntheses of thiadiazoleine and thiadiazolee derivatives by the cyclization of 3-aryl-4-formylsydnone thiosemicarbazons with acetic anhydrid and ferric chloride”, Tetrahedron, 61, 10917–10925 29 Mei-Hsiu Shih, Fang-Ying Ke (2004), “Syntheses and evaluation of antioxidant activity of sydnonyl substituted thiazolidinone and thiazoline derivatives”, Bioorg Med Chem., 12, 4633-4643 30 Mei-Hsiu Shih, Mou-Yung Yeh (2003), “Access to the syntheses of sydnonylsubstituted α,β-unsaturated ketones and 1,3-dihydro-indol-2-ones by modified Knoevenagel reaction”, Tetrahedron, 59, 4103-4111 31 Mitragotri S.D., Pore D.M., Desai U.V., Wadgaonkar P.P (2008) Sulfamic acid: An efficient and cost-effective solid acid catalyst for the synthesis of aminophosphonates at ambient temperature, Catal Commun., 9, 1822–1826 32.Moonen K., Laureyn I and Stevens C V (2004), “Synthetic Methods for Azahetherrocyclic Phosphonates and Their Biological Activity”, Chem 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(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the(LUAN.van.THAC.si).nghien.cuu.tong.hop.mot.so.peracetyl.Ỵ².d.glucopyranosyl.thiosemicarbazon.cua.4.acetylsydnone.the 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