u tng ht s 4- acetylsydnone tetra-O-acetyl--D- galactopyranosyl thiosemicarbazon th  H i hc Khoa hc T  Lu ThS.  ; : 60 44 27 ng dn: PGS.TS. Nguy o v: 2012 Abstract. Tng hp cht 3-(R-      -(R-  -nitroso-N-(R-  ng. Chuyp cht 4-acetyl-3-(R-n xut 4-bromacetyl-3- (R-ng. Tng hp cht 2--(tetra-O-acetyl- -D-galactopyranosyl-amino)]-5--arylsydnone)-6H-1,3,4-  u c  h c  p cht 2--(tetra-O-acetyl--D- galactopyranosylamino)]-5--arylsydnone)-6H-1,3,4- sinh hc cng hc. Keywords. ; Hp cht h; Hoc Content p cht u hoc bit  c th-thiadiazin  ho hc     p chng chim v  c h  p nh kh  n cng, c ch s n hoc dit tr c dnh.    -oxadiazoli-5-                               ng.  thiadiazin     thiosemicarbazid   thiadiazin,  “         -acetylsydnone tetra-O-acetyl--D- ”    N-phenyl sydnone    .       -carbon(C 4      C 4 -   ~1730cm 1  O N N O Ph O N N O Ph O N N O Ph O N N O Ph 1.52 1.37 1.64 1.64 1.41 1.64 -0.88 +0.19 +0.03 +0.03 -0.34 +0.73 -0.71 +0.24 +0.11 +0.21 -0.43 +0.57 -0.35 +0.08 +0.01 +0.35 -0.14 +0.3 2 3 4 5 Hình 1.1. Biểu diễn điện tích trong vòng sydnone. - 3     3  4  4, O 1, O 6  5    3   5-Aryl-1,3,4-thiadiazin  . -thiadiazin    2-Morpholino-5-phenyl- 6H-1,3,4-thiadiazin  -thiadiazin-diethyldipyrazolyl disulfide      .        - dimethylamino-5-phenyl-6H-1,3,4-thiadiazin-6-5500.08     N,N-dimethyl-5-phenyl-1,3,4-thiadiazol-2-amin   N N S Ph O N S N NMe 2 Ph 550 °C, 0.008 Torr -CO + + Me 2 N-CN PhCN 9 1-(Benzensulfonyl)-3-phenylnaphtho[2,3-e]1,3,4-thiadiazin-5,10-diol (10)    -(benzensulfonyl)-3-phenyl-1H-benzo[f]indazole-4,9-un  N N S O O SO 2 Ph Ph O O N N SO 2 Ph Ph t°, toluen -S 10 11 1,3,4-thiadiazin    (20)   1 =H, MeEt, Ar, COOEt, Ac; R 2 =H, Alk,Ar; R 3 =NHAlk, NHAr, NMe 2  (21)  -thiadiazin  1,3,4-thiadiazin      -thiadiazin          N N S R 1 R 2 R 3 N H N R 1 R 2 R 3 H + -S 20 21      - -3-methyl-2,3-dihydro-6H-1,3,4-thiadiazin(22) (23)      -phenyl-  -ethoxycarbonyl-6H-1,3,4-thiadiazin(20) (R 2  H-1,3,4-thiadiazin -40% 5-imino-1,2-   N N S Ph NR Me N N Ph NHR Me H + -S 22 23 N N S Ph NMe Me Me N N Ph NMe Me Me H + -S 24 25         -carboxy6-phenyl-2-phenylimino- 6H-1,3,4-thiadiazin(26)  (27)     -diphenyl-2,7-diphenylimino-1H,6H-dipyrazolo[1,5-- d]pyrazin (28). NH N H S HOOC NPh Ph N H N HOOC NHPh 26 27 PPA -S N N N H N H O O Ph PhN NPh Ph 28       -thiadiazin       -          -thiadiazin              -imino-  -alkylimino-5-methyl-6H-1,3,4- thiadiazin-amino- -[alkyl(aryl)amino]-4-methyl-2,3- dihydro-1,3-thiazole (30). NH N S R 1 NH 2 + R 2 H 29 N S R 1 NH 2 NH 2 + R 2 30 5-Methyl-6H-1,3,4-thiadiazin(31) (R 1    -nitrobenzaldehyd (R 2 =H, NO 2   acid, thu  -(benzylideN-  -[(4-nitrobenzylidene)hydrazino]thiazole (32). NH N S NH 2 + R 1 H CH 3 31 N S CH 3 NH 2 NH R 1 N CH C 6 H 4 -4-R 2 32 2-Amino- -alkylamino-5-phenyl-6H-1,3,4-thiadiazin(33)     -alkylimino-3-methyl-4-phenyl-2,3-dihydro-6H-1,3,4-thiadiazin(34)   --2-imino-5-methyl-2,3-dihydro-6H-1,3,4-thiadiazin    -amino-5- methyl-6H-1,3,4-thiadiazin   N N S NHR 2 R 1 Ph 33 N N S Ph CH 3 NR 2 R 1 34 Mel, Me 2 CO t°, 10h 2-Dialkylamino-5-aryl-6H-1,3,4-thiadiazin 1,3,4-thiadiazin        -dialkylamino-6H-1,3,4- thiadiazin            dimethyl sulfoxide -pyrrolidino- -cyclohexylamino-5-phenyl-6H-1,3,4-thiadiazin -dialkylamino- 5-phenyl-6H-1,3,4-thiadiazin N N S Ph R 1 N N + S Ph R 1 R 2 35 X - Me 2 CO MeSO 3 F or EtOBF 4 t°, 0.5-6h 6H-1,3,4-thiadiazin-2(3H)-    2    -thiadiazoles (36).  + N-   2 . NH N S R 2 O R 1 N N S R 2 R 1 36 ButOCl,DMF, 0 °C -CO 2  6H-1,3,4-thiadiazin-2-amin (37) -halogen keton cho 2H- imidazo[2,1-b]6H-1,3,4-thiadiazin(38) (R 1 =Ar; R 2 =H). N N S Ph NH 2 + R 2 Br O R 1 -HBr, -H 2 O N N S N Ph R 2 R 1 37 38 N N H S CH 3 Ph CH 3 MeCOOC N S HOOC Ph NH NHAc N S MeCOOC Ph NH NH 2 N S MeCOOC Ph NH N CH 3 CH 3 N N S MeOOC Ph NH 2 HCl Me 2 CO CF 3 CO 2 H 55 - 60 °C 60 61  -         phn ng v  n xut ca acid thiocarbamic cho ng.   4 -       2   2 , phm 1956[21].  -mercapto-1,3,4-thiadiazol. Ph sau:   DMF, d                                                              -  1  Năng lượng photon vi sóng trong vùng tần số này (0,0016 eV), quá yếu để phá vỡ liên kết hoá học và cũng thấp hơn năng lượng của chuyển động Brownn  hiệu ứng nhiệt của các vật liệu nhờ hiệu ứng nhiệt điện môi vi sóng    sự làm phân cực và sự truyền ion.   4-BROMOACETYL-3-(R-PHENYL)SYDNONE -bromoacetyl-3-(R-phenyl)sydnone em  -acetyl-3-(R-phenyl) acetyl -  N-(R- oacetat. - N-(R-  N-nitroso-N-(R-phenyl)glycine. - -(R-N-nitroso-N-(R-phenyl)glycine  -   -(R-phenyl)sydnone     2 O 5    -        -acetyl-3-(R-phenyl)sydnone   percloric HClO 4 510C. - bromo  N-(R-phenyl)glycine N-(R-phenyl)glycine em N-   Phương pháp 1:N-(R-phenyl)     N-(R-phenyl)glycine    N-(R-phenyl)glycine. Phương pháp 2;      Phương pháp 3:               N-(R-phenyl)glycine N-nitroso-N-(R-phenyl)glycine N-nitroso-N-(R-phenyl)glycine N-(R-phenyl)glycine  th- 2-N-(R-phenyl)glycine         -(R-phenyl)sydnone        N-nitroso-N-(R-phenyl)   anhyd         3-(R-phenyl)sydnone.          -acetyl-3-(R-phenyl)sydnone. -acetyl-3-(R-phenyl)sydnone       “phương pháp nóng” “phương pháp lạnh” Phương pháp nóng          2 O 5       acetic    m 96 0  Phương pháp lạnh 10 4    15 30-  em       2 O 5  c    dunn-hexan : ethy -bromoacetyl-3-(R-phenyl)sydnone            bromo      20 .      =   2        10   15-20 .  2 ,                             ,    .            2        , cho   ,          ,        .       --(tetra-O-ACETYL--D- GLACTOPYRANOSYLAMINO)-5--ARYLSYDNONE)-6H-1,3,4-THIADIAZIN          -79      o    n-hexan          2-3          .4. Bảng kết quả tổng hợp và dữ kiện vật lý của 2-(2’,3’,4’,6’-(tetra-O-acetyl-β-D- galactopyranosylamino)-5-(3”-arylsydnone)-6H-1,3,4-thiadiazin N R Màu sắc Hiệu suất(%) Đ nc (°C) 7a H  75 107,2-108,1 7b 4-Me  80 123,7-124,5 7c 2-Me  78 158,2-158,9 7d 4-MeO  72 124,4-124,6 7e 4-Cl  75 161,3-161,8 7f 4-Br  76 130,9-131,3 V    P CHT --(TETRA-O-ACETYL--D- GALACTOPYRANOSYLAMINO)-5--ARYLSYDNONE)-6H-1,3,4-THIADIAZIN - Phổ hồng ngoại. [...]... synthesis of sydnonyl-R-imidazoles”, Tetrahedron 63, pp 29902999 20 Mei-Hsiu Shiha and Mou-Yung Yeh (2003), “ Access to the synthesises of sydnonyl-R-a,b-unsaturated ketones and 1,3-dihydro-indol-2-ones by modified Knoevenagel reaction”, tetrahedron 59, pp 41 03 -41 11 21 Mei-Hsiu Shih and Fang-Ying Ke (20 04) , “Syntheses and evaluation of antioxidant activity of sydnonyl Rthiazolidinone and thiazoline derivatives”,... and Miron teodor Caproiu.(2006), “New pyrazoles by 1,3dipolar cycloaddition reactions between sydnones and activated alkynes”, Revue Roumaine de Chinie, 51 (4) , 255-260 10 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, pp 641 3- 642 4... Kazusato Kanda, Akiko Chinone, and Masaki Ohta.(1973), “Reaction of 4- acetylsydnones”, Bulletin of the chemical society of Japan, vol 46 , pp 33 04- 3306 12 HsieN-Ju Tien, Jong-Chuan Yeh and Shi-Chen Wu (1992), “Acetylation and debromination of sydnones accelerated by ultrasound”, Journal of the chinese chemiscal society, 39, pp 44 3 -44 7 13 HsieN-JuTien, Mou-Yung Yeh and ChuN-Yin Huang (1985), “A study of... các 3-arylsydnone thế nhận được, đã điều chế được 6 hợp chất 4- acetyl- 3arylsydnone bằng phản ứng acetyl hoá khi sử d ng acid acetic bằng với sự có mặt của P 2O5 hoặc anhydrid acetic với sự có mặt của acid percloric, từ đó tổng hợp được 4- bromoacetyl-3aryl sydnone tương ứng 2 Đã tổng hợp được 6 hợp chất 2-(2’,3’ ,4 ,6’- (tetra- O- acetyl- β- D- galactopyranosyl amino)-5(3”-arylsydnone)-6H-1,3 ,4- thiadiazinbằng... thesydnone compounds: bromination and chlorination(III)”, J Chin Chem Soc., 32, pp 46 1 -46 5 14 HsieN-J tui en, Shaw-Tao Lin and Jin N-Stair Sheu (19 94) , “Nitration of 3-aryl -4- acetylsydnones: preparation of 3(3-nitroaryl)sydnones by using acetyl group as ablocking group”, J Chem 72, pp 1610-1613 15 K.P.Srivastava and P.K.Mỉhra (2009), “Green synthesis of 4- acetyl- 3- (4- R-) phenyl sydnones under microwave... phổ ứng d ng trong hoá học–NXB Khoa học Kỹ thuật, Hà Nội Tài liệu tiếng Anh: 2 Asha Budakoti, Mohammad Abid and Amir Azam, Assony S J (1961), “The chemistry of isothiocyanat”, Organic chemistry of sulfur compounds, Ed Kharasch N, Oxford, Vol 9, pp 326327 3 BrowneD.L., Harrity J.P.A.(2010), “Recent developments in the chemistry of sydnone”, Tetrahedron, 66, pp 553-568 4 Budakoti A., Abid M and Azam A... 4- alkynyl-Rsydnone”, Mendeleev Commun., 7, pp 93- 94 7 Christopher G Newton and Christopher A Ramsden (1982), “Meso-ionic hetherrocycles”, Tetrahedron, vol 38, No 20, pp 2965-3011 8 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), pp 9 548 -9551 9 Florea Dumitrascu, Constantin Draghici, Daniela...Phổ hồng ngoại của 2-(2’,3’ ,4 ,6’ -tetra- O- acetyl- β- D- galactopyranosylamino)-5-[3’’-(4bromophenyl)sydnone]-6H-1,3 ,4- thiadiazin Bảng băng sóng hấp phụ phổ IR của các hợp chất2-(2’,3’ ,4 ,6’ -tetra- O- acetyl- D- galactopyranosylamino)-5-(3’’-arylsydnone)-6H-1,3 ,4- thiadiazin N0 R γNH γC =O (ester) γC -O- C (ester) γC=C γC=N 7a H 3321 1 748 1222, 1058 1505, 1520 1600 7b 4 ’’-Me 3328 1 746 1228, 1053 1512, 147 0 1630... 3alkoxy(phenyl)thiophosphorylamido-2-(per -O- acetyl- D- glycopyranosyl-1’imino)thiazolidine -4- one derivatives from O- alkyl N4glycosyl(thiosemicarbazido)phosphonothionates”, Carbohydr Res., 3 34, pp 1 248 1253 33 Yu Xin Li, Zheng Ming Li, Wei Guang Zhao, Wen Li Dong, Su Hua Wang (2006), “Synthesis of novel 1Arylsunfonyl -4- (1’-N-2’,3’ ,4, 6’ -tetra- O- acetyl- β- Dglucopyranosyl)thiosemicarbazides”, Chin Chem Lett., 17(2), pp 153-155 ... derivatives”, Bioorganic and medicinal chemistry, pp 46 33 -46 43 22 Lech Stefaniak (1977), “14NNMR study of some sydnones, sydnonimines and delated structures”,Tetrahedron Vol 33, pp 2571-2575 23 Shreenivas R Deshpande, K Vasantakumar Pai (2010), “Synthesis , Antibacterial and Analgesic Activity of 4- [1Oxo-3-(R-aryl)-2-propenyl]-3- (4- methylphenyl)sydnones”, E-J ournal of Chemistry, 7(1), pp 59- 64 24 Shanta .   - alkoxy(phenyl)thiophosphorylamido-2-(per -O- acetyl- D- glycopyranosyl-1  - imino)thiazolidine -4- one derivatives from O- alkyl N 4 - . -- (TETRA- O- ACETYL-  -D- GALACTOPYRANOSYLAMINO)-5--ARYLSYDNONE)-6H-1,3 ,4- THIADIAZIN - Phổ hồng ngoại. Phổ hồng ngoại của 2-(2 ’ ,3 ’ ,4 ’ ,6 ’ -tetra- O- acetyl- β- D- galactopyranosylamino)-5-[3 ’’ - (4- bromophenyl)sydnone]-6H-1,3 ,4- thiadiazin.