• Title/Summary/Keyword: Thiazine

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Conversion of 1,3-Thiazolidines to Dihydro-1,4-thiazine by Chlorinolysis

  • Lee, Wha-Suk;Mah, He-Duck;Nam, Kee-Dal;Kang, Soon-Bang
    • Bulletin of the Korean Chemical Society
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    • v.13 no.1
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    • pp.83-87
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    • 1992
  • The ring expansion of 1,3-thiazolidines 4 derived from ${\beta}$-ketoacid derivatives to the corresponding dihydro-1,4-thiazines 1 by using the action of chlorine on 4 has been achieved. In the chlorinolysis unisolable sulfenyl chlorides 5 may be formed from chlorosulfonium ions 11 by ${\beta}$-elimination involving carbonyl activated methylene hydrogens. Addition of sulfenyl chloride to the internal double bond appears to form probable thiiranium ions 14, which in turn gave 1 with loss of acidic proton. Imminium ions 15 could be hydrolyzed easily to give enol 8. As a side reaction, dihydrothiazine that was formed was further chlorinated to produce dichlorides 16 which were rearranged readily to the chloromethyl compounds 10.

Activated Nitrites in Heterocyclic Synthesis: Syntheses of Thiazole, Pyrazole and 4H-l,4-Benzothiazine Derivatives

  • El-Taweel, Fathy Mohamed Abdel-Aziz;Hadi-Mashaly, Mohamed-Abdel;Ali-Elagamey, Abdel-Ghani
    • Archives of Pharmacal Research
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    • v.13 no.3
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    • pp.261-264
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    • 1990
  • 4-Arylazo-3-phenyl-5-aminopyrazoles (5a, b) and substituted hydroxythiazoles 8a, b were synthesized from the reaction of 4a, b with hydrazine hydrate and mercaptoacetic acid respectively. Compounds 5a, b and 8a, b were also obtained from coupling of 2a, b with 6 and 7, respectively. 4H-1, 4-Benzothiazine 11 was prepared from 1 and 10. The resaction of the diazonium salts 2a-c with diethyl 3-amino-2-cyanopenet-2-en-1, 5-dicarboxylate 12 was also reported.

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A Study on the Stereochemistry of 1,3-Thiazolidine (1,3-티아졸리딘 술폭시드의 입체구조에 관한 연구)

  • Ma He-Duck;Park Shin-Ja;Han Hoh-Gyu
    • Journal of the Korean Chemical Society
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    • v.37 no.1
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    • pp.119-130
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    • 1993
  • The stereochemistry of 1,3-thiazolidine sulfoxides 1 in which 3 chiral centres are present in a molecule was elucidated by deuterium exchange and trapping reactions. 3-Acetoxy-1,3-thiazolidines 5 was oxidized to 6 and 8, corresponding $\alpha$-cis 10, $\alpha$-trans 11, $\beta$ -cis 12, and $\beta$ -trans 13 isomers were separated from their diasteromeric mixtures. Sulfoxide 10 was isomerized to more thermodynamically stable isomer 13 under neutral conditions in refluxing benzene or toluene. The methyl hydrogens of 2-methyl group in the sulfoxide 13 and those of the sulfoxide 11 were deuterated by the deuterium incorporation reactions. The intermediate sulfenic acids 25 and 26 derived from the sulfoxides 10 and 12 via sigmatropic rearrangement were trapped by 2-mercaptobenzothiazole (2-MBT) to give disufides 27 and 28 respectively. However, the sulfoxides 11 and 13 were transformed to ring expansion product dihydro-1,4-thiazine 29 under the same reaction conditions. In the presence of acid catalyst, the sulfoxides 10, 11, and 12 were converted to dihydro-1,4-thiazine 29 through the sulfoxide 13 quantitatively. The mechanisms of isomerization of sulfoxides and the formation of 29 were also discussed.

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A Case of Acute Dapsone Poisoning Complicated with Methylene Blue-induced Hemolytic Anemia (급성 댑손 중독 환자에서 메틸렌블루 치료중 유발된 메트헤모글로빈혈증과 중증 용혈성 빈혈 1례)

  • Lee, Mi-Jin;Park, Kyu-Nam
    • Journal of The Korean Society of Clinical Toxicology
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    • v.4 no.2
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    • pp.170-174
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    • 2006
  • Methylene blue is a basic thiazine dye frequently used for histologic staining. In clinical toxicology settings, it is also used to treat clinically significant methemoglobinemia. It has dose-dependent oxidation or reduction properties, acting as a reducing agent at lower doses and as an oxidizing agent at higher doses. Hemolytic anemia and hyperbilirubinemia are known toxic effects of methylene blue treatment that have been reported clinically. A 42-year-old woman developed significant methemoglobinemia after acute dapsone overdose; she was treated appropriately with intravenous methylene blue in the therapeutic range. The patient's methemoglobin levels returned to normal. However, 2-4 days later she was noted to have rebound methemoglobinemia, hemolytic anemia, and hyperbilirubinemia. A repeat of Coomb's test and other anemia workups were negative. For management of methylene blue-induced hemolytic anemia, she was administered steroid therapy, N-acetylcysteine, and a blood transfusion. She ultimately recovered, and there were no long-term sequelae from the methylene blue poisoning.

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Electroluminesent Properties of Phenothiazyl Derivatives Having Aromatic Moieties

  • Kim, Soo-Kang;Kang, In-Nam;Park, Jong-Wook;Kim, Kyoung-Soo;Choi, Cheol-Kyu;Lee, Sang-Do
    • Journal of Information Display
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    • v.7 no.4
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    • pp.9-12
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    • 2006
  • This paper reports the synthesis and electroluminescent properties of new aromatic compounds as hole-transporting materials based on phenothiazine, such as 1,4-diphenothiazyl-benzene [DPtzB], 1,4-diphenothiazyl-xylene [DPtzX] and 9,10-diphenothiazyl-anthracene [DPtzA]. DPtzB thin film exhibited photoluminescence (PL) maximum emission peak and emission shoulder at 450 and 475 nm, and a maximum emission at 447 nm without emission shoulder was obtained in DPtzX thin film. When DPtzA was excited by incident light of 359 nm, DPtzA showed strong PL emission at 417 nm and weak emission at 600 nm. Luminance efficiency of DPtzB, DPtzX and DPtzA-based electroluminescence (EL) devices was 3.57, 3.46 and 0.47 cd/A, and power efficiency of DPtzB, DPtzX and DPtzA-based EL devices was 1.48, 1.26 and 0.201 m/W.

Studies on the Characteristics of Humic Acid and Its Utilization (V). Manufacturing of Sulfur-dyes from Humic Acid (土炭흄산의 性狀 및 應用에 關한 硏究(第 5 報). 황化染料 製造)

  • Han Kyoungsuk;Kim Wontaik
    • Journal of the Korean Chemical Society
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    • v.19 no.1
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    • pp.65-70
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    • 1975
  • Sulfur-dyes were manufactured from humic acid, $Na_2S_{2~3}$ and other additives at $200{\sim}250^{\circ}C$ for 3∼20 hrs. Sulfur-dyes from humic acid were fundamentally brown colors and could be changed from yellowish to grayish brown according to the additives. The colorfastness to rubbing and laundering were excellent but to weather was fair. Characteristic bonds of sulfur-dyes such as -C-S-C, -C-SO-C-. -C-$SO_2$-C-, and -C-O-$SO_2$-O-C- were confirmed but thiazole bond and thiazine ring were not done by IR-spectroscopy.

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The Solvent-Independent Structure of Piroxicam (피록시캄의 용매 비의존 결정구조)

  • Kim, Bong-Hee;Suh, Il-Hwan;Jhee, Ok-In;Suh, Jong-Myung;Suh, Jung-Jin
    • Journal of Pharmaceutical Investigation
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    • v.18 no.4
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    • pp.209-215
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    • 1988
  • The three-dimensional structures of piroxicam crystallized from two different solvents, toluene and toluene/hexane mixture respectively, are proved identical: $C_{15}H_{13}N_3O_4S,\;M\;=\;331.35$, monoclinic, a = 7.128(1), b = 15.146(2), c = 13.956(2) ${\AA},\;{\beta}=\;97.33(1)^{\circ},\;V\;=\;1494.37{\AA}^{3},\;Dx\;=\;1.472\;g/cm^{3},\;Z\;=\;4,\;space\;group\;P2_{1}/c,\;Mo\;K{\alpha}(\lambda=\;0.71073\;{\AA})$, F(000) = 688, T = 295 K, R = 0.0611 for 1993 unique observed reflections. The thiazine ring exhibits a half chair conformation. An amide group is involved in an intramolecular hydrogen bond to the hydroxy group, O(17)-H(17)${\cdots}O(15){\AA}$. The molecule is planar within 2 ${\AA}$ with the interplanar angle $127.9(4)^{\circ}$ between pyridine and benzene rings. A molecular chain parallel to [011] is formed by two intermolecular hydrogen bonds N(16)-H(6)${\cdots}O(11)$ and C(6)-H(6)${\cdots}O(11)$, and the molecular chains are held together by van der Waals forces.

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Studies on the Synthesis and Antibacterial Activities of 7-Thiazinylcephalosporin Derivatives (7-티아지닐 세파로스포린 유도체의 합성과 생리활성에 관한 연구)

  • Lee, Young-Haeng;Chai, Kyu-Yun;Hyang, Sun-Am;Choi, Won-Sik
    • YAKHAK HOEJI
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    • v.41 no.4
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    • pp.473-479
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    • 1997
  • New cephalosporin antibiotics, 7-[(3,4-dihydro-6-methoxycarbonyl-2,2-dimethyl-2H-1,4-thiazin-3-yl)acetamido]-3-substituted-3-cephem-4-carboxylic acid derivatives 2a-2d, 7 -[(3,4-dihydro-6-ethoxycarbonyl-2,2-dimethyl-2H-1,4-thiazin-3-yl)acetamido] -3-substituted-3-cephem-4-carboxylic acid derivatives 3a-3d and 7-[(3,4-dihydro-6-methoxycarbonyl-2,2-dimethyl-2H-1,4-thiazin-3-yl-1-(S)-oxide)acetamido]-3-substituted-3-cephem-4-carboxylic acid derivatives 4a-4d were synthesized. Antibacterial activities of these new cephalosporin derivatives and the relationship between their structures and their activities were examined. Among them, 7-[(3,4-dihydro-6-methoxycaronyl-2,2-dimethyl-2H-1,4-thiazin-3-yl-1-(S)oxide)-acetamido]-3-[(1,2,3-triazol-5-yl)thiomethyl]-3-cephem-4-carboxylic acid 4d exhibited the antibacterial activities against Gram(+)and Gram(-) bacteria.

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The Study on the Thyroglobulin in Thyroid Diseases (갑상선질환(甲狀腺疾患)의 Thyroglobulin에 관(關)한 연구(硏究)(예보(豫報)))

  • Kim, Suk-Keun;Lim, Soo-Duk;Lee, Mun-Ho
    • The Korean Journal of Nuclear Medicine
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    • v.4 no.1
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    • pp.43-49
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    • 1970
  • In recent years with development of immuno-electrophoresis, more acurate analysis of the serum protein became possible. However, there is few reports in the literature which investigated the changes of the immunoglobulin compared with electrophoretically fractioned serum thyroglobulin in the patients with various thyroid diseases. The purpose of this report is to investigate the changes of thyroglobulin in various thyroid diseases by the method of immuno-electrophoresis and to compare the results with.serum protein fractionated by the method of agar-gel micro-electrophoresis. Materials and Methods: Sera from 9 patients with diffuse toxic goiter, 2 nodular nontoxic goiter, 2 thyroiditis, 3 hypothy, roidism, 1 thyroid cancer, 7 cystic degeneration of the thyroid gland, and 10 normal subject were taken. All cases were confirmed by various laboratory thyroid function tests and thyroid needle biopsy. Immuno-electrophoretic analysis of the serum were performed by Scheidegger's modified micro-immuno-electrophoretic method. The antiserum was obtained from the Travenol Laboratories International, Hyland Products Division and was rabbit anti-human thyroglobulin. Microscope slide agar-gel electrophoresis for serum protein fractionation was performed at $4^{\circ}C$ using veronal buffer, pH 8.6 and ionic strength 0.05, with 54 volts and 2.8 mA for 60 minutes. The fractionated slide was stained with 0.1% thiazine red. The results were as follows: 1) Increase of immune-globulin macroglobulin (IgM), alphaglobulin, and immune-globulin A (IgA) by 95.8%, 100%, 29.2% respectively was found in the serum from various thyroid diseases. 2) Thyroglobulin fraction was found to be increased in 50%, no change in 41.7%, and no line in 8.3% with all of the various goiter patients. On the other hand, 10 normal control group showed only 2 cases of increase, 5 cases of no change and 3 cases of no line.

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Reduction of nitro blue tetrazolium by combined reaction of various photosensitizers with amino acids (다양한 감광제와 아미노산의 조합 반응에서 nitro blue tetrazolium의 환원특성 평가)

  • Lee, Eunbin;Hong, Jungil
    • Korean Journal of Food Science and Technology
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    • v.54 no.1
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    • pp.1-7
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    • 2022
  • Riboflavin (Rb), in the presence of methionine (Met) under light, generates superoxide radicals that can reduce nitro blue tetrazolium (NBT) to its corresponding formazan. The Rb-Met/NBT system has been used to measure the superoxide dismutase (SOD)-like activities of various antioxidants. However, the reaction mechanisms have not been clearly defined, and the assay conditions are not consistent. In this study, the effects of different photosensitizers and amino acids on NBT reduction in different solvents were investigated. NBT reduction in the Rb-Met/NBT system was more pronounced in phosphate-buffered saline, compared to distilled water or Tris (pH 7.5); histidine (His) instead of Met also led to considerable Rb-induced NBT reduction. Among the photosensitizers, methylene blue with His caused potent NBT reduction in Tris. Rb-induced NBT reduction combined with Met or His was quantitatively inhibited by SOD or gallic acid, but did not affect MB-induced reduction sensitively.