Halides and oxide halides of technetium. I. Technetium(V) oxide halides and the reaction of thionyl chloride with ammonium pertechnetate

1968 ◽  
Vol 21 (8) ◽  
pp. 1981 ◽  
Author(s):  
R Colton ◽  
IB Tomkins

Chlorination of technetium dioxide has been shown to give technetium oxide trichloride as the major product. The presence of an unstable second product, thought to be the oxide tetrachloride, was confirmed. Bromination of technetium dioxide gives only technetium oxide tribromide. Thionyl chloride reacts with ammonium pertechnetate to give ammonium dioxotetrachlorotechnetate(V1), which was isolated as its sulphuryl chloride adduct, (NH4),[TcO2Cl4],SO2Cl2.

1971 ◽  
Vol 24 (5) ◽  
pp. 1009 ◽  
Author(s):  
JM Coxon ◽  
MP Hartshorn ◽  
AJ Lewis

Reaction of the r-2-hydroxy-2-phenyl-c-3-p-tolylsulphonyloxybornanes (4b) and (10b) with base gave the epimeric 2,3-epoxy-2-phenylbornanes (1) and (2). Acid-catalysed rearrangement of the endo-epoxide (2) gave 2-endo-phenylbornan-3-one (8); similar reaction of the exo-epoxide (1) afforded the unsaturated aldehyde (6) as the major product. Pyrolysis of the cyclic sulphites (16) and (17), prepared from the 2,3-exo-diol (4a) by reaction with thionyl chloride, gave mixtures of 2-endo- phenylbornan-3-one (8) and the aldehyde (5).


1979 ◽  
Vol 32 (4) ◽  
pp. 833 ◽  
Author(s):  
CM Bonnin ◽  
PA Cadby ◽  
CG Freeman ◽  
AD Ward

3,4-Dialkoxy-substituted phenylpropiolic acids and esters react with thionyl chloride to give good yields of substituted 1-benzothiophen systems. Similar reactions of m-and p-methoxyphenylpropiolic acids and 3,4,5-trimethoxyphenylpropiolic acid, which yield mixtures of products, are reported. In contrast, 2,5- and 2,3-dimethoxyphenylpropiolic acids gave mixtures in which a coumarin is the major product. The effect of adding pyridine to the reaction mixture is outlined. Reactions involving sulfur monochloride and sulfur dichloride generally gave much lower yields of these products. Attempts to form organometallic intermediates from the 3-chloro-1-benzothiophen products were unsuccessful.


1961 ◽  
Vol 36 (4) ◽  
pp. 511-519 ◽  
Author(s):  
Margaret Wiener ◽  
Charles I. Lupa ◽  
E. Jürgen Plotz

ABSTRACT 17α-hydroxyprogesterone-4-14C-17α-caproate (HPC), a long-acting progestational agent, was incubated with homogenates of rat liver and human placenta. The rat liver was found to reduce Ring A of HPC under anaerobic conditions to form allopregnane-3β,17α-diol-20-one-17α-caproate and pregnane-3β,17α-diol-20-one-17α-caproate, the allopregnane isomer being the major product. The caproic acid ester was neither removed nor altered during the incubation. Placental tissue did not attack HPC under conditions where the 20-ketone of progesterone was reduced. It is postulated that this absence of attack on the side chain is due to steric hindrance from the caproate ester, and that this may account for the prolonged action of HPC.


1999 ◽  
Vol 40 (6) ◽  
pp. 45-51 ◽  
Author(s):  
Andrea M. Dietrich ◽  
Susan Mirlohi ◽  
Willian F. DaCosta ◽  
Jennifer Peters Dodd ◽  
Richard Sauer ◽  
...  

Reactions of iodine and phenol were investigated to determine which iodophenols were produced and their odor properties. The research was performed in support of the USA space program that applies iodine to disinfect potable water for spacecraft use. Higher concentrations (50 mg/l) and higher iodine:phenol (e.g. 10:1) ratios resulted in the formation of greater iodophenol concentrations and higher substituted iodophenols. The reactions were fast and nearly complete within 1 hour. For pH 5.5 and 8 and all iodine:phenol ratios, formation of monosubstituted compounds indicated that 2-iodophenol was favored over 4-iodophenol. At the intermediate iodine:phenol ratios of 1:1 and 2:1, substantial amounts of the diiophenols formed and persisted for up to 32 days. The diiodophenols were not detected at iodine:phenol ratios of 0.2:1 and 10:1. The compound 2,4,6-triiodophenol was the major product formed at a 10:1 iodine:phenol ratio and the formation of this trisubstituted phenol appeared nearly complete. Odor evaluation indicated that the iodophenols have much lower odor threshold concentrations (OTC) than phenol. The 2- and 4- iodophenol had OTC values of ≅ 1 and 500 μg/l, respectively, with odors described as “medicinal, phenol, chemical”.


2019 ◽  
Vol 12 (3) ◽  
pp. 247-255 ◽  
Author(s):  
Dheyauldeen Shabeeb ◽  
Mansoor Keshavarz ◽  
Alireza Shirazi ◽  
Gholamreza Hassanzadeh ◽  
Mohammed Reza Hadian ◽  
...  

Background: Radiotherapy (RT) is a treatment method for cancer using ionizing radiation (IR). The interaction between IR with tissues produces free radicals that cause biological damages.As the largest organ in the human body, the skeletal muscles may be affected by detrimental effects of ionizing radiation. To eliminate these side effects, we used melatonin, a major product secreted by the pineal gland in mammals, as a radioprotective agent. Materials and Methods: For this study, a total of sixty male Wistar rats were used. They were allotted to 4 groups: control (C), melatonin (M), radiation (R) and melatonin + radiation (MR). Rats’ right hind legs were irradiated with 30 Gy single dose of gamma radiation, while 100 mg/kg of melatonin was given to them 30 minutes before irradiation and 5 mg/ kg once daily afternoon for 30 days. Five rats in each group were sacrificed 4, 12 and 20 weeks after irradiation for histological and biochemical examinations. Results: Our results showed radiation-induced biochemical, histological and electrophysiological changes in normal rats’ gastrocnemius muscle tissues. Biochemical analysis showed that malondialdehyde (MDA) levels significantly elevated in R group (P<0.001) and reduced significantly in M and MR groups after 4, 12, and 20 weeks (P<0.001), However, the activity of catalase (CAT) and superoxide dismutase(SOD)decreased in the R group and increased in M and MR groups for the same periods of time compared with the C group (P<0.001), while melatonin administration inverted these effects( P<0.001).Histopathological examination showed significant differences between R group for different parameters compared with other groups (P<0.001). However, the administration of melatonin prevented these effects(P<0.001). Electromyography (EMG) examination showed that the compound action potential (CMAP) value in the R group was significantly reduced compared to the effects in the C and M groups after 12 and 20 weeks (P<0.001). The administration of melatonin also reversed these effects (P<0.001). Conclusion: Melatonin can improve biochemical, electrophysiological and morphological features of irradiated gastrocnemius muscle tissues.Our recommendation is that melatonin should be administered in optimal dose. For effective protection of muscle tissues, and increased therapeutic ratio of radiation therapy, this should be done within a long period of time.


1984 ◽  
Vol 49 (1) ◽  
pp. 110-121 ◽  
Author(s):  
Jiří Křepelka ◽  
Drahuše Vlčková ◽  
Milan Mělka

Alkylation of derivatives of 4-aryl-1-naphthols (I-V) by 2,3-epoxypropyl chloride in methanolic sodium hydroxide gave epoxy derivatives VI, VIII, IX, XI and XII, apart from products of cleavage of the oxirane ring, VII and X. Analogous alkylation of compounds I, IV and V by 2-(N,N-diethylamino)ethyl chloride hydrochloride in a two-phase medium afforded basic ethers XIII to XV. The cleavage of the oxirane ring in compound VI by the action of primary and secondary amines, piperidine and substituted piperazines led to compounds XVI-XXIV. Reaction of thionyl chloride with compounds XXI, XXII and XXIV gave chloro derivatives XXV-XXVII.Exposure of compound XXII to 4-methylbenzenesulfonyl chloride produced compound XXVIII, retaining the secondary alcoholic group. In an antineoplastic screening in vivo none of the compounds prepared had an appreciable activity. Compound XVII, being an analogue of propranolol, was used in the test of isoproterenolic tachycardia, and showed a beta-lytic effect comparable with that of propranol.


1986 ◽  
Vol 51 (10) ◽  
pp. 2167-2180 ◽  
Author(s):  
Lubor Fišera ◽  
Nadezhda D. Kozhina ◽  
Peter Oravec ◽  
Hans-Joachim Timpe ◽  
Ladislav Štibrányi ◽  
...  

3-Aryl-4-R-carbamoyl-5-hydroxymethylisoxazolines (IV) were synthesized by allowing R-NH2 amines with R = H, CH3, C3H7, C6H5C2H5, and NH2 to act on 3-(X-phenyl)-4-oxo-3a,4,6,6a-tetrahydrofuro[3,4-d]isoxazoles (III) with X = H, 4-CH3, 4-OCH3, 2-OCH3, 4-Cl, 2-Cl, 4-F, 2-F, 4-Br, 4-NO2, and 3-NO2. Exposed to radiation, the substances IV give Z-2-hydroxymethylamino-2-aryl-1-formylacrylamides (V) in good yields. The 4-Cl and 4-F substituted Z-derivatives V isomerize irreversibly to the E-derivatives VI if allowed to stand in solvent; the remaining derivatives V are stable. The quantum yields of the photoreaction are from 0.012 to 0.106 in dependence on the substituent X. In all cases where the compounds IV were used for the preparation of condensed heterocycles in conditions of acid-catalyzed reactions, lactones III were preferentially formed; the action of thionyl chloride on IV results in the formation of chloromethyl derivatives VIII, which do not undergo further cyclization.


1997 ◽  
Vol 62 (7) ◽  
pp. 1114-1127 ◽  
Author(s):  
Hubert Hřebabecký ◽  
Jan Balzarini ◽  
Antonín Holý

3'-Chloro and 3'-acetylsulfanyl derivatives of 1-(2-deoxy-4-C-hydroxymethyl-α-L-threo-pentofuranosyl)uracil were prepared by reaction of 2,3'-anhydro-1-{5'-O-benzoyl-4'-C-[(benzoyloxy)methyl]-2'-deoxy-α-L-erythro-pentofuranosyl}uracil (3) with hydrogen chloride and thioacetic acid, respectively. The reaction with hydrogen chloride gave a mixture of N-1 and N-3 substituted uracil derivatives 12 and 14. Reaction of 1-{3-O-benzoyl-4-C-[(benzoyloxy)methyl]-2-deoxy-α-L-threo-pentofuranosyl}uracil (7) with thionyl chloride and subsequent debenzoylation afforded 1-(4-C-chloromethyl-2-deoxy-β-D-erythro-pentofuranosyl)uracil (19). Nucleophilic substitution with lithium thioacetate, followed by deacylation, converted 1-{3-O-benzoyl-4-C-[(benzoyloxy)methyl]-2-deoxy-5-O-p-toluenesulfonyl-α-L-threo-pentofuranosyl}uracil (9) into 1-(2-deoxy-4-C-sulfanylmethyl-β-D-erythro-pentofuranosyl)uracil (21). The obtained thiols were oxidized with iodine or air to give 1,1'-[disulfandiylbis(2,3-dideoxy-4-hydroxymethyl-α-L-threo-pentofuranose-3,1-diyl]di(pyrimidine-2,4-(1H,3H)-dione) (17) and 1,1'-[disulfandiylbis(2,5-dideoxy-4-hydroxymethyl-α-L-threo-pentofuranose-5,1-diyl]di(pyrimidine-2,4(1H,3H)-dione) (22). Reaction of 1-{3-acetylsulfanyl-5-O-methanesulfonyl-4-C-[(benzoyloxy)methyl]-2,3-dideoxy-α-L-threo-pentofuranosyl)}uracil (24) with methanolic sodium methoxide afforded 1-(3,5-anhydro-2,3-dideoxy-4-C-hydroxymethyl-3-sulfanyl-α-L-threo-pentofuranosyl)uracil (25). The same reagent was used in the preparation of 1-(3,5-anhydro-2-deoxy-4-C-hydroxymethyl-α-L-threo-pentofuranosyl)uracil (26) from 1-{4-C-[(benzoyloxy)methyl]-2-deoxy-5-O-p-toluenesulfonyl-α-L-threo-pentofuranosyl}uracil (8). From the series of 4'-substituted 2'-deoxyuridine derivatives, synthesized in this study, solely the 4'-chloromethyl derivative 19 and the oxetane derivative 26 exhibited an appreciable activity against HIV-1 and HIV-2.


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