Potential antihistamine agents: 4-(6,11-Dihydrodibenzo[b,e]thiepin-11-ylidene)-1-methyltetrahydrothiopyranium iodide and similar sulfonium salts derived from related tricyclic systems

1987 ◽  
Vol 52 (11) ◽  
pp. 2758-2774 ◽  
Author(s):  
Zdeněk Polívka ◽  
Jiří Holubek ◽  
Miloš Buděšínský ◽  
Oluše Matoušová ◽  
Emil Svátek ◽  
...  
Keyword(s):  
Methyl Iodide ◽  
Methyl Derivative ◽  
Sulfonium Salt ◽  
Sulfonium Salts ◽  
Central Effects ◽  
Tertiary Alcohols ◽  
Antihistamine Activity ◽  
Grignard Reactions ◽  
By Products

Thioxanthone, 10,11-dihydrodibenzo[a,d]cyclohepten-5-one, dibenzo[b,e]thiepin-11(6H)-one, its 2-methyl derivative, and thieno[2,3-c]-2-benzothiepin-4(9H)-one were reacted with 4-tetrahydrothiopyranylmagnesium bromide and the obtained tertiary alcohols IVabc, VIc, and XIX were dehydrated to the olefinic sulfides IXabc, Xc, and XXI. Addition of methyl iodide afforded the title compounds XIabc, XIIc, and XXII. The Grignard reactions were accompanied by the 1,6-addition giving the ketones XVI-XVIII as by-products. The reductive properties of tetrahydrothiopyranylmagnesium bromide were most striking in the case of reaction with 2-chlorothioxanthone; the isolation of thioxanthene and thioxanthone showed that nuclear dehalogenation took also place. Reactions of 11-chloro-6,11-dihydrodibenzo[b,e]thiepin and benzhydryl chloride with tetrahydrothiopyran-4-ol gave the sulfides XXV and XXVIII; whereas the latter reacted with methyl iodide under the formation of sulfonium salt XXIX, the former was cleaved and gave 4-hydroxyl-1-methyltetrahydrothiopyranium iodide (XXVI). The sulfonium salts are free of the central effects but their antihistamine activity is rather low.

6,11-Dihydrodibenzo[b,e]thiepin-11-yl 3-quinuclidinyl ethers: New potential intidepressants and antihistamine agents

1988 ◽  
Vol 53 (8) ◽  
pp. 1806-1811 ◽  
Author(s):  
Zdeněk Polívka ◽  
Jan Metyš ◽  
Miroslav Protiva
Keyword(s):  
Methyl Derivative ◽  
Antihistamine Activity ◽  
Antidepressant Agent ◽  
Anticataleptic Activity

Reactions of 11-chloro-6,11-dihydrodibenzo[b,e]thiepin and its 2-methyl derivative, and further of the methanesulfonates of 2-chloro- and 2-bromo-6,11-dihydrodibenzo[b,e]thiepin-11-ol with 3-quinuclidinol afforded the title ethers I-IV. The 2-methyl compound II (VÚFB-17 088) showed significant antihistamine activity and the 2-chloro compound III (VÚFB-17 089), having antireserpine and anticataleptic activity, proved a potential antidepressant agent.

Self-radiation induced exchange between tritiated water and organic compounds. The labelling of L-chiro-inositol, myo-inositol and Hexa-O-methyl-L-chiro-inositol

1975 ◽  
Vol 28 (9) ◽  
pp. 1981 ◽  
Author(s):  
DHT Fong ◽  
CL Bodkin ◽  
MA Long ◽  
JL Garnett
Keyword(s):  
Organic Compounds ◽  
Radiochemical Purity ◽  
Specific Activity ◽  
Tritiated Water ◽  
High Specific Activity ◽  
Methyl Derivative ◽  
Radiation Induced ◽  
By Products ◽  
Gas Exposure

The stereochemistry of the tritiation of L-chiro-inositol, myo-inositol and hexa-O-methyl-L-chiro-inositol by self-radiation induced exchange with tritiated water of high specific activity has been investigated. Predominance of configurational retention was found to accompany tritium labelling in the two inositols, while substantial configurational inversion occurred in the hexa-O-methyl derivative. Tritiation occurred predominantly at C 1 in L-chiro-inositol, with slight inversion at this position alone accompanying the labelling. Comparison with Wilzbach T2 gas exposure results indicates the HTO method yields less by-products, myo-inositol having a radiochemical purity of 97%.

Sulfonamide Analogues of Creatinine. The Synthesis of 3-Amino-4,5-dihydro-1,2,4-thiadiazole 1,1-Dioxides from Base-Induced Cyclization Reactions

1997 ◽  
Vol 50 (10) ◽  
pp. 1027 ◽  
Author(s):  
Fares A. Fares ◽  
Damon D. Ridley ◽  
Ping Yin
Keyword(s):  
Methyl Iodide ◽  
Cyclization Reactions ◽  
Methyl Derivative

We report the preparation of 3-amino-4,5-dihydro-1,2,4-thiadiazole 1,1-dioxide and of its 4-methyl derivative which are of interest as potential analogues of creatinine. The thiadiazoles are obtained from chloromethylsulfonylation ofS-benzylisothiourea, followed by cyclization of the chloromethanesulfonamide under basic conditions in the presence of 2-(t-butoxycarbonyloxyimino)-2-phenylacetonitrile or of methyl iodide.

Polynuclear Gold(I) Complexes of Mercaptocarboxylic Acids

1996 ◽  
Vol 51 (6) ◽  
pp. 765-772 ◽  
Author(s):  
Alexander Sladek ◽  
Wolfgang Schneider ◽  
Klaus Angermaier ◽  
Andreas Bauer ◽  
Hubert Schmidbaur
Keyword(s):  
Functional Model ◽  
Crystal Structure Analysis ◽  
Water Soluble ◽  
Carboxyl Groups ◽  
Gold Content ◽  
Reference Compound ◽  
Tertiary Phosphine ◽  
Sulfonium Salt ◽  
Sulfonium Salts ◽  
Acid Function

Abstract In a search for air-stable and water-soluble mercapto compounds of gold with a high gold content, benzylthiol, a-m ercapto-acetic acid, β-mercapto-propionic acid, and thiosalicylic acid were converted into aurated sulfonium salts by treatment with reagents of the type [(R3P)Au]3O+ BF4- or [(R3)P)Au]+ BF4-. - BzSH served as a mono-functional model thiol, which was converted into BzS[Au(PMe3)]2+ BF4- (1). The small tertiary phosphine was chosen in order to minimize steric effects. In the crystal the cations are associated into centrosymmetrical dimers through short Au-A u contacts (auriophilicity). - The two carboxylic acids with thiol functions, HSCH2COOH and HSCH2CH2COOH, gave triply aurated species of the type {[(Ph3P)Au]2S(CH2)nCOOAu(PPh3)}+ BF4- (2: n = 2, 3; n = 3). The crystal structure analysis of the representative compound 2 showed again the presence of centrosymmetrical cation dimers with geometrical details of the sulfonium part of the molecules very similar to those of the reference compound 1. In addition, the carboxyl groups in 2 and 3 bear a (phosphine)gold unit mono-hapto bound at one of the oxygen atoms. -2-HS-C6H4-COOH was converted into a sulfonium salt {[(Ph3P)Au]2S-C6H4-COOH}+ BF4- (4), which crystallizes free of solvent from dry dichloromethane, and as a monohydrate with one mole of dichloromethane (4a = 4 H2O-CH2CI2) from hydrous CH2CI2. In the solvent-free crystalline phase (4) the cations are associated into dimers with the usual intermolecular double A u-A u contacts, but in 4a there are monomeric cations with the water molecule hydrogen-bonded to the carboxylic acid function

scholarly journals SULFONIUM SALT SOLVOLYSIS: PART V. MODEL SYSTEMS FOR BIOLOGICAL TRANSMETHYLATION

1965 ◽  
Vol 43 (1) ◽  
pp. 57-63 ◽  
Author(s):  
James B. Hyne ◽  
James H. Jensen
Keyword(s):  
Model Systems ◽  
Carboxyl Group ◽  
Sulfonium Salt ◽  
Sulfonium Salts

The rates of solvolysis of a series of sulfonium salts which may be considered as models for the biologically important sulfonium salt, S-adenosylmethionine, are discussed in terms of a possible anchimeric role of the carboxyl group of methionine in transmethylation reactions.

scholarly journals Synthesis of Functionalised Cyclohexanes from Carbohydrates

2021 ◽  
Author(s):  
◽  
Regine Blattner
Keyword(s):  
Hydrogen Cyanide ◽  
Reductive Elimination ◽  
Hydroxyl Groups ◽  
Reaction Sequence ◽  
Tertiary Alcohols ◽  
Carbocyclic Compounds ◽  
Branched Chain ◽  
By Products ◽  
Tertiary Hydroxyl ◽  
Bromo Compound

<p>Beta-D-glucopyranose pentaacetate was photobrominated to give the 5-baromide from which 6-deoxy-Beta-D-xylo-hex-5-enopyranose tetraacetate was obtained by reductive elimination. This reaction sequence represents an efficient new route to the 5-ene. A detailed investigation into the photobromination of Beta-D-glucopyranose pentaacetate with bromine and with NBS led to the isolation of several by-products containing bromine substituents at C-1 and/or C-5; their reactions with zinc-acetic acid were studied, and the conformations. in solution of four alkenes derived from the 5-bromo compound were determined. 2,3,4-Triacylated 2,3,4,5-tetrahydroxycyclohexanones were Obtained by mercury (II) catalysed rearrangement of 5-deoxyhex-5-enopyranose esters. The mechanism of this rearrangement, and some enopyranose esters The mechanism of this rearrangement, reactions of the products were examined. The use of these new carbocyclic compounds in the synthesis of branched-chain cyclitol derivatives was explored. By means of diazomethane or, alternatively, hydrogen cyanide, substituted cyclohexanes with one-carbon branches and tertiary hydroxyl groups at the site of chain-branching were preared. Attempts to eliminate water from these tertiary alcohols to give substituted cyclohexene-carbonitriles or -carbaldehydes were unsuccessful.</p>

Recent Advances on Annulation Reactions with Allyl and Propargyl Sulfonium Salts

Synthesis ◽  
2021 ◽  
Author(s):  
Qing-Zhu Li ◽  
Wen-Lin Zou ◽  
Zhi-Qiang Jia ◽  
Jun-Long Li
Keyword(s):  
Building Blocks ◽  
Sulfonium Salt ◽  
Comprehensive Overview ◽  
Sulfonium Salts ◽  
Recent Advances ◽  
Recent Developments ◽  
Sulfur Ylide

Allyl and propargyl sulfonium salts are readily available reagents and have recently emerged as versatile building blocks in the assembly of cyclic skeletons. As an alternative to the classical sulfonium salts, allyl and propargyl sulfonium salts can convert to the corresponding vinyl sulfur ylide or allenic sulfonium salt intermediates that contain diverse nucleophilic or electrophilic reactive positions, thereby enabling a great variety of annulation reactions. In this review, we provide a comprehensive overview of the recent developments on this growing field by summarizing the annulation reactions involving allyl and propargyl sulfonium salts.

Antihistamine activity and central effects of WAL 801 CL in man

1987 ◽  
Vol 33 (4) ◽  
pp. 381-385 ◽  
Author(s):  
W. S. Adamus ◽  
J. Oldigs-Kerber ◽  
H. F. Lohmann
Keyword(s):  
Central Effects ◽  
Antihistamine Activity

Derivatives of the Benzo[5,6]cyclohepta[1,2,3-Cd]thieno[3,2-C]pyridine System. X-Ray Crystal Structure of 8,9-Dimethoxy-1,2,3,6,11,11a-hexahydrobenzo[5,6]cyclohepta[1,2,3-Cd]thieno[3,2-C]pyridine-1-carbonitrile

1988 ◽  
Vol 41 (4) ◽  
pp. 575 ◽  
Author(s):  
JB Bremner ◽  
EJ Browne ◽  
LM Engelhardt ◽  
BA Hyland ◽  
GS James ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Crystal Structure ◽  
Cyanogen Bromide ◽  
Heterocyclic System ◽  
Crystal And Molecular Structure ◽  
Ring Cleavage ◽  
Methyl Derivative ◽  
X Ray ◽  
Derivatives Of ◽  
By Products

During attempts to prepare 9,10-dimethoxy-4,7,12,12a-tetrahydro-5H- benzo [g] thieno [3,2-a] quinolizine (1), and subsequent cyanogen bromide- induced ring cleavage of this tetracyclic base, two by-products were isolated. The preparations of these two compounds are described, and their structures elucidated as 8,9-dimethoxy-1,2,3,6,11,11a-hexahydrobenzo [5,6] cyclohepta [1,2,3-cd] thieno [3,2-c]pyridine (5a), and its 1-carbonitrile derivative (5b). An N-methyl derivative (5c) has been prepared from (5a). These products (5) are the first examples of a new heterocyclic system. The crystal and molecular structure of the cyanamide (5b) has been determined by X-ray crystallographic methods.

scholarly journals Free radicals in synthesis. Clean reagents affording oxidative or reductive termination

2000 ◽  
Vol 72 (7) ◽  
pp. 1327-1334 ◽  
Author(s):  
John A. Murphy
Keyword(s):  
Polar Group ◽  
Hypophosphorous Acid ◽  
Sulfonium Salts ◽  
Oxidative Functionalization ◽  
Radical Chemistry ◽  
Alkyl Radicals ◽  
Aryl Radicals ◽  
Tributyltin Hydride ◽  
Alkyl Bromides ◽  
By Products

Neurotoxic organotin reagents currently play a key role in radical chemistry. As a result, this is an important area for development of new clean replacement reactions. The pharmaceutical industry in particular has had to avoid use of radical methodology for the formation of carbon_carbon bonds for this reason. With the current dawn in green chemistry, a host of new clean radical methods is beginning to flourish. Our aim has been to develop new nontoxic methodology for carbon_carbon bond formation by radical chemistry, which would provide either reductive termination (giving a hydrogen atom to the ultimate radical, as happens with tributyltin hydride), or oxidative functionalization, installing a useful polar group at the site of the ultimate radical. Two methods for effecting radical reactions in an environmentally friendly way are presented: (i) The tetrathiafulvalene (TTF)-mediated radical-polar crossover reaction converts arenediazonium salts to aryl radicals, which have sufficient lifetime to cyclize onto alkenes—the resulting alkyl radicals couple with TTF+• to afford sulfonium salts which, in turn, undergo solvolysis to alcohols, ethers or amides. The method provides the key step in a synthesis of (±)-aspidospermidine. (ii) Hypophosphite salts and hypophosphorous acid, on the other hand, form C_C bonds with reductive termination. These economical reagents afford radicals efficiently, starting from aryl iodides, alkyl bromides, and alkyl iodides, and give very easy separation of products from by-products.

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