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The synthesis of heterocyclic analogues of the platelet activating factor is described.The preparation starts with acylating rac-tetrahydro-1,3-thiazine-4-carboxylic acid ethyl ester, with palmitoyl chloride to form the amide linkage.Following ester reduction, the phosphocholine part is introduced via 2-chloro-2-oxo-1,3,2-dioxaphospholane and subsequent ring opening with trimethylamine under pressure.Furthermore, the related L-thiazolidine analogue is prepared using the same procedure.In addition the sulfinyl and sulfonyl derivatives of this compound are obtained by oxidation with 3-chloro-perbenzoic acid.From one sulfinyl intermediate the diastereomeres are separated and their conformations are determined by 13C-NMR spectroscopy. Keywords: Phospholipid synthesis; Cyclic platelet activating factor analogue; Cyclic thioether; Chiral sulphur compound

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The reaction of ferrocene with methyl or ethyl esters of L-cysteine in the presence of paraformaldehyde is studied. This process yields the optically pure derivatives: methyl or ethyl (R)-3-(ferrocenylmethyl)thiazolidine-4-carboxylates (1a or 1b), together with the corresponding N,N-bisthiazolidine derivatives (2a or 2b). When the reaction was carried out using the ethyl ester of L-cysteine, small amounts (ca. 9%) of the 1,1′-disubstituted ferrocene derivative (3b) were also isolated. The reactivity of compounds 1 versus palladium(II) species is studied, and has allowed us to isolate and characterise: [Pd(eta3-C3H5)Br(1a)] (4a) and [Pd(eta3-C3H5)Br(1b)] (4b), in which the ferrocenyl ligand behaves as a monodentate S-donor group. Compounds 4 evolve in the presence of dimethylsulfoxide to produce: [Pd(eta1-C3H5)Br(1)(dmso)] (5) in which the palladium(II) is bound to the terminal carbon of the C3H5 group. The reactivity of ligands 1 with Na2[PdCl4] is also reported and has allowed us to isolate the dinuclear compounds [Pd2Cl4(mu-1a)2] (6a) and [Pd2Cl4(mu-1b)2] (6b)] in which the thiazolidine behaves as a bridging (N,S) donor group.

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The synthesis of heterocyclic analogues of the platelet activating factor is described. The preparation starts with acylating rac-tetrahydro-1,3-thiazine-4-carboxylic acid ethyl ester, with palmitoyl chloride to form the amide linkage. Following ester reduction, the phosphocholine part is introduced via 2-chloro-2-oxo-1,3,2-dioxaphospholane and subsequent ring opening with trimethylamine under pressure. Furthermore, the related L-thiazolidine analogue is prepared using the same procedure. In addition the sulfinyl and sulfonyl derivatives of this compound are obtained by oxidation with 3-chloro-perbencoic acid. From one sulfinyl intermediate the diastereomeres are separated and their conformations are determinated by 13C-NMR spectroscopy.

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Certain new phosphonoalkanoylamino acids of the formula (I) herein and their pharmaceutically acceptable salts exhibit improved antihypertensive properties and are parti-cularly useful for the reduction of angiotensin related hypertension. in which R? and R?, which are the same or different, are each selected from the group consisting of a hydrogen atom, an optionally substituted lower alkyl, a lower alkenyl, an optionally substituted aryl and an optionally substituted aralkyl radical; n is 0 or 1; R? is a hydrogen atom, an optionally substituted lower alkyl, a lower alkenyl, an optionally substituted aryl or an optional-ly substituted aralkyl group; and (a) R? is a hydrogen atom, a lower alkyl or a phenyl-lower alkyl radical; R? and R?, which are the same or different, are each selected from the group consisting of a hydrogen atom, an optionally substituted lower alkyl or an aryl radical; and R? is selected from the group consisting of-OR?,-NR? or-SR??, wherein R? and R?? are each selected from the group consisting of a hydrogen atom, a lower alkyl, an optionally substituted aryl, or an optionally substituted aralkyl radical and R? is a hydrogen atom, a hydroxy or lower alkyl radical or the residue of an-amino acid; or (b) R? and R? are part of a four-, five-or six-membered optionally substituted heterocyclic ring as a connected bridge of 2 to 4 atoms of carbon or carbon and either nitrogen, sulphur or oxygen; and R? and R? are each as defined in (a); with the proviso that when R? is a hydrogen atom, n is 0, the heterocyclic ring is an unsubstituted pyrrolidine, R? is a hydrogen atom, and R? is OR?, at least one of R?, R? and R? is an optionally substituted aryl radical; or (c) R? and R? are selected to form a side chain of alpha-amino acid, where N(R?) CR?R?COR? is an alpha-amino acid residue; with the proviso that (i) when R? is hydrogen and n is 0, the

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Treatment of L-cysteine esters and thiazolidine-4-carboxylic esters with an excess of paraformaldehyde in the presence of trifluoroacetic acid provides C2-symmetric N,N?-methylene-bisthiazolidines in good yield.

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Methyl and ethyl 3-alkylthiazolidine-4(R)-carboxylates (1-6 and 7-12), which were newly synthesized, inhibited growth of the roots of Brassica campestris L. subsp. rapa Hook fil. et Anders.Of the methyl esters, methyl 3-methylthiazolidine-4(R)-carboxylate (2) was the strongest inhibitor.Of the ethyl esters, ethyl 3-methylthiazolidine-4(R)-carboxylate (8) was the strongest inhibitor.The chlorophyll concentration in the cotyledons of plants treated with any of the compounds, except for 7, was decreased.

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The reaction of ferrocene with methyl or ethyl esters of L-cysteine in the presence of paraformaldehyde is studied. This process yields the optically pure derivatives: methyl or ethyl (R)-3-(ferrocenylmethyl)thiazolidine-4-carboxylates (1a or 1b), together with the corresponding N,N-bisthiazolidine derivatives (2a or 2b). When the reaction was carried out using the ethyl ester of L-cysteine, small amounts (ca. 9%) of the 1,1′-disubstituted ferrocene derivative (3b) were also isolated. The reactivity of compounds 1 versus palladium(II) species is studied, and has allowed us to isolate and characterise: [Pd(eta3-C3H5)Br(1a)] (4a) and [Pd(eta3-C3H5)Br(1b)] (4b), in which the ferrocenyl ligand behaves as a monodentate S-donor group. Compounds 4 evolve in the presence of dimethylsulfoxide to produce: [Pd(eta1-C3H5)Br(1)(dmso)] (5) in which the palladium(II) is bound to the terminal carbon of the C3H5 group. The reactivity of ligands 1 with Na2[PdCl4] is also reported and has allowed us to isolate the dinuclear compounds [Pd2Cl4(mu-1a)2] (6a) and [Pd2Cl4(mu-1b)2] (6b)] in which the thiazolidine behaves as a bridging (N,S) donor group.

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The synthesis of heterocyclic analogues of the platelet activating factor is described. The preparation starts with acylating rac-tetrahydro-1,3-thiazine-4-carboxylic acid ethyl ester, with palmitoyl chloride to form the amide linkage. Following ester reduction, the phosphocholine part is introduced via 2-chloro-2-oxo-1,3,2-dioxaphospholane and subsequent ring opening with trimethylamine under pressure. Furthermore, the related L-thiazolidine analogue is prepared using the same procedure. In addition the sulfinyl and sulfonyl derivatives of this compound are obtained by oxidation with 3-chloro-perbencoic acid. From one sulfinyl intermediate the diastereomeres are separated and their conformations are determinated by 13C-NMR spectroscopy.

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Certain new phosphonoalkanoylamino acids of the formula (I) herein and their pharmaceutically acceptable salts exhibit improved antihypertensive properties and are parti-cularly useful for the reduction of angiotensin related hypertension. in which R? and R?, which are the same or different, are each selected from the group consisting of a hydrogen atom, an optionally substituted lower alkyl, a lower alkenyl, an optionally substituted aryl and an optionally substituted aralkyl radical; n is 0 or 1; R? is a hydrogen atom, an optionally substituted lower alkyl, a lower alkenyl, an optionally substituted aryl or an optional-ly substituted aralkyl group; and (a) R? is a hydrogen atom, a lower alkyl or a phenyl-lower alkyl radical; R? and R?, which are the same or different, are each selected from the group consisting of a hydrogen atom, an optionally substituted lower alkyl or an aryl radical; and R? is selected from the group consisting of-OR?,-NR? or-SR??, wherein R? and R?? are each selected from the group consisting of a hydrogen atom, a lower alkyl, an optionally substituted aryl, or an optionally substituted aralkyl radical and R? is a hydrogen atom, a hydroxy or lower alkyl radical or the residue of an-amino acid; or (b) R? and R? are part of a four-, five-or six-membered optionally substituted heterocyclic ring as a connected bridge of 2 to 4 atoms of carbon or carbon and either nitrogen, sulphur or oxygen; and R? and R? are each as defined in (a); with the proviso that when R? is a hydrogen atom, n is 0, the heterocyclic ring is an unsubstituted pyrrolidine, R? is a hydrogen atom, and R? is OR?, at least one of R?, R? and R? is an optionally substituted aryl radical; or (c) R? and R? are selected to form a side chain of alpha-amino acid, where N(R?) CR?R?COR? is an alpha-amino acid residue; with the proviso that (i) when R? is hydrogen and n is 0, the

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Treatment of L-cysteine esters and thiazolidine-4-carboxylic esters with an excess of paraformaldehyde in the presence of trifluoroacetic acid provides C2-symmetric N,N?-methylene-bisthiazolidines in good yield.

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