Konfigurative Zuordnung über sterisch definierte Epoxydringe, IV. Spaltungsreaktionen des (±)‐<i>cis</i>‐ und (±)‐<i>trans</i>‐1‐Phenyl‐2‐methyl‐äthylenoxyds

Fischer, Friedrich; Rönsch, Hasso

doi:10.1002/cber.19610940406

Cited by 14 publications

(4 citation statements)

References 6 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The iodide-catalyzed rearrangement of the formerly mentioned compounds provides a method for preparing the tetrahydroimidazoimidazole system: Ethyleneimine reacts with epoxides to form hydroxyalkylated products, eg, N-(β-hydroxyethylaziridine) [1072-52-2]. The epoxide component is frequently used in substoichiometric amount in order to prevent multiple alkoxylation (180)(181)(182)(183)(184)(185)(186)(187)(188)(189)(190). Ethyleneimine and episulfides react to give complex product mixtures, since the 1-(2mercaptoethyl)aziridine produced initially can easily react further with both reactants (191,192).…”

Section: Reaction Of Cyanuric Chloride [108-77-0] With Ethyleneimine mentioning

confidence: 99%

Imines, Cyclic

Scherr¹,

Steuerle²,

Fikentscher³

2000

Kirk-Othmer Encyclopedia of Chemical Technology

View full text Add to dashboard Cite

show abstract

Section: Reaction Of Cyanuric Chloride [108-77-0] With Ethyleneimine mentioning

confidence: 99%

Imines, Cyclic

Scherr¹,

Steuerle²,

Fikentscher³

2000

Kirk-Othmer Encyclopedia of Chemical Technology

View full text Add to dashboard Cite

show abstract

“…248 nm) spectra further confirmed the structure.Oxidation of methyl 6-phenylhex-5-enoate (42) (E: Z ca. 80:20) with MCPBA in methylene chloride gave the expected mixture of trans-and cis-epoxides(8). The 'H n.m.r.…”

mentioning

confidence: 96%

“…There appear to be no studies of the reactions of thiols with P-substituted styrene oxides. We report here some reactions of the P-methylstyrene oxides (4F (7) with thiols, preparatory to similar reactions of methyl 6-phenyl-5,6-epoxyhexanoate (8) which are also described.…”

mentioning

confidence: 99%

“…Although the diastereoisomeric mixtures (54) and (55) could not be separated chromatographically or crystallized and the reaction of ethyl cysteine (32) with the epoxide failed to give well defined products [cf: trans-P-methylstyrene oxide (4)], we believe these preliminary results are encouraging. Further investigation of the reactions of the epoxide (8) with cysteine and its other derivatives (e.g. methyl N-trifluoroacetylcysteine) and with glutathione and its derivatives are proposed.…”

mentioning

confidence: 99%

See 1 more Smart Citation

Regiochemistry of nucleophilic opening of β-substituted styrene oxides with thiolate anions: model experiments in the synthesis of leukotriene analogues

Marples¹,

Saint²,

Traynor³

1986

J. Chem. Soc., Perkin Trans. 1

View full text Add to dashboard Cite

Leics. LEI 7 3TUP-Substituted trans-styrene oxides are cleaved with thiolate anions highly regioselectively by attack at the a-carbon whereas the cis-isomers are cleaved by attack at the a-and P-carbons. Cysteine, in a suitably protected form, similarly cleaves P-substituted trans-styrene oxides, thus allowing the synthesis of a simple LTE model. Slow reacting substances, e.g., leukotriene C, (l), are recognized as important regulators of the immune response and are mediators, inter aka, of airways constriction and bronchial spasm in human asthma.'-3 The possibility that analogues of leukotrienes may be useful antagonists is attractive and we have sought to synthesize simple models (2) of leukotriene E,, in which an aromatic ring may be regarded as replacing the 7,9diene system in a cisoid conformation.It was expected that the models (2) might easily be prepared by the addition of cysteine to the epoxides (3). The addition of simple thiols to styrene oxide has been studied4 and there are a number of reports 5-12 of the additions of other nucleophiles to styrene oxides and some of their P-substituted derivatives.In general, the regiochemistry of such reactions is determined by the substitution of the phenyl ring, the stereochemistry of the epoxide, and the reaction conditions. There appear to be no studies of the reactions of thiols with P-substituted styrene oxides. We report here some reactions of the P-methylstyrene oxides (4F(7) with thiols, preparatory to similar reactions of methyl 6-phenyl-5,6-epoxyhexanoate (8) which are also described.Additions to P-Methylstyrene Oxides.-The trans-epoxides (4) and (6) l 3 were prepared by MCPBA oxidation of (E)-Pmethylstyrene and by treatment of 4-methoxy-P-methylstyrene successively with HOBr and KOH.14 The cis-epoxidest (5) and (7)9 were prepared by MCPBA oxidation of the (97methylstyrenes which were obtained by reaction of the aromatic aldehyde with the ylide derived from ethyltriphenylphosphonium bromide. The peracid oxidation of (Z)-4-methoxy-Pmethylstyrene was carried out in methylene chloride-aqueous sodium hydrogen carbonate. 'Reaction of the trans-epoxides (4) and (6) with thiophenoltriethylamine and the similar reaction of (4) with toluene-athiol-triethylamine gave only the erythro-products (9), (lo), and (1 1) respectively, of nucleophilic attack at the a-carbon. The mass spectra of the adducts (9)-(11) showed important fragment ions at m/z 199,229, and 213, respectively, corresponding to the ions (15), (16), and (17) and demonstrating the attachment of the sulphur atom to the a-carbon. The base peaks in the mass spectra of ( 9 H l l ) at m/z 200,165, and 91 are assigned to the ions (18), (19), and the tropyllium ion respectively. It is presumed that the ion (18) arises by a hydrogen transfer process with loss of acetaldehyde. The equivalent ion m/z 214 is quite intense in the mass spectrum of the adduct (11). Further support for the regiochemistry of the adducts comes from their 'H n.m.r. spectra and those of the acetates (12)--(14). For example in the 'H n.m....

show abstract

Ethylene Oxides

Rosowsky¹

1964

Chemistry of Heterocyclic Compounds: A Series of Monographs

View full text Add to dashboard Cite

Konfigurative Zuordnung über sterisch definierte Epoxydringe, IV. Spaltungsreaktionen des (±)‐cis‐ und (±)‐trans‐1‐Phenyl‐2‐methyl‐äthylenoxyds

Cited by 14 publications

References 6 publications

Imines, Cyclic

Imines, Cyclic

Regiochemistry of nucleophilic opening of β-substituted styrene oxides with thiolate anions: model experiments in the synthesis of leukotriene analogues

Ethylene Oxides

Contact Info

Product

Resources

About