Nghiên cứu tổng hợp và chuyển hóa một số 4 acetylsydnone tetra o acetyl β d galactopyranosyl thiosemicarbazon thế

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. 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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.