Preparation of some deuterium labelled 9- and/or 10-oxygenated derivatives of geraniol, geranial, nerol, and neral

1983 ◽  
Vol 61 (6) ◽  
pp. 1053-1059 ◽  
Author(s):  
J. Balsevich
Keyword(s):  
Selective Oxidation ◽  
Wittig Reaction ◽  
Dimethyl Acetal ◽  
Acidic Hydrolysis ◽  
Triphenyl Phosphonium ◽  
Isomeric Purity ◽  
Derivatives Of

The preparation of various deuterium labelled 9- and/or 10-oxygenated derivatives of geraniol, geranial, nerol, and neral is described. Wittig reaction of the tetrahydropyranyl ethers of (E)- and (Z)-1,1-dideutero-6-(triphenylphosphonium)-3-methyl-2-hexen-1-ol iodides (23 and 24) with the tetrahydropyranyl ethers of hydroxyacetone and 1,3-dihydroxyacetone afforded, after deprotection, C-1 dideuterated 9-hydroxygeraniol, 9-hydroxynerol, 9,10-dihydroxygeraniol, and 9,10-dihydroxynerol of high isomeric purity. Selective oxidation of these products allowed for the preparation of the corresponding derivatives possessing an aldehyde functionality at C-9 or C-1 and C-9. Wittig reaction of 23 and 24 with pyruvaldèhyde dimethyl acetal followed by acidic hydrolysis afforded C-1 dideuterated 10-oxogeraniol and 10-oxonerol, oxidation of which yielded C-1 deuterated 10-oxogeranial and 10-oxoneral. Wittig reaction of (E)- and (Z)-1,1-dideutero-6-(triphenyl-phosphonium)-3-methyl-2-hexen-1-ol iodides (49 and 50) with 1,1,3,3-tetraethoxyacetone afforded C-1 dideuterated 9,9,10,10-tetraethoxygeraniol and 9,9.10,10-tetraethoxynerol, oxidation of which provided C-1 deuterated 9,9,10,10-tctraethoxygeranial and 9,9,10,10-tetraethoxyneral.

X-ray crystal structure analysis of a bisepoxide derived from secologanin: the structure and absolute configuration

1983 ◽  
Vol 61 (2) ◽  
pp. 282-283 ◽  
Author(s):  
Stanley C. Nyburg ◽  
Pik Y. Siew ◽  
Gavin N. Saunders ◽  
John R. Purdy ◽  
Stewart McLean
Keyword(s):  
Crystal Structure ◽  
Structure Analysis ◽  
Absolute Configuration ◽  
Dimethyl Acetal ◽  
Crystal Structure Analysis ◽  
Side Chain ◽  
Bench Mark ◽  
Chemical Transformations ◽  
X Ray ◽  
Derivatives Of

The structure and absolute configuration of a bisepoxide (2) produced by oxidation of tetraacetylsecologanin dimethyl acetal (1) with m-chloroperbenzoic acid have been established by X-ray crystal structure analysis. Epoxidation of the vinyl side chain is unexceptional; epoxidation of the β-alkoxyacrylate moiety is novel. This determination represents a valuable bench mark for configurational assignments, since the bisepoxide has been correlated by chemical transformations with a number of synthetic and naturally-occurring derivatives of secologanin.

Synthesis and reactions of β-substituted derivatives of furan

1985 ◽  
Vol 50 (9) ◽  
pp. 2077-2083 ◽  
Author(s):  
Adolf Jurášek ◽  
Vladimír Žvak ◽  
Jaroslav Kováč ◽  
Oľga Rajniaková ◽  
Jarmila Štetinová
Keyword(s):  
Wittig Reaction ◽  
Cycloaddition Reaction ◽  
Uv Spectra ◽  
H Nmr ◽  
Spectral Evidence ◽  
Derivatives Of

The 1,4-cycloaddition reaction of 4-phenyl-1,3-oxazole to 2-propinyl benzoate and dimethyl butinedioate afforded the respective 3-furylmethyl benzoate (I) and 3,4-bis(methoxycarbonyl)furan (II). These compounds served for the synthesis of 3-chloromethylfuran and 3,4-bis(chloromethyl)furan, which afforded via Wittig reaction 3-(β-arylvinyl)furans III (aryl = 5-nitro-2-furyl (IIIa), 5-nitro-2-thienyl (IIIb), 1-methyl-4-nitro-2-pyrrolyl (IIIc), and 4-nitrophenyl (IIIe)) and 3,4-bis(β-arylvinyl)furans IV (aryl = 5-nitrofuryl (IVa), 5-nitro-2-thienyl (IVc), and 4-nitrophenyl (IVd)). According to spectral evidence (1H NMR, IR, UV spectra), compound IIIa and IIIb originated as E isomers, whilst the remaining products are a mixture of E and Z isomers; some couples were succeded to separate.

Wittig type reactions of 2-formylated derivatives of 6-methylergoline - I

1982 ◽  
Vol 47 (6) ◽  
pp. 1636-1640 ◽  
Author(s):  
Jan Beneš ◽  
Jiří Holubek
Keyword(s):  
Wittig Reaction ◽  
Sodium Hydride ◽  
Ethyl Esters ◽  
Acrylic Acids ◽  
Derivatives Of

Using the Horner-Wittig reaction, aldehydes I and II were converted, with high E-selectivity, into ethyl esters of substituted acrylic acids, VI and VII. The N-anions generated by deprotonation of derivative I-V with sodium hydride in tetrahydrofuran reacted with vinyltriphenylphosphonium bromide with the formation of derivatives of pyrrolo[1,2-a]ergoline-I, XI-XV.

Selective oxidation of O-isopropylidene derivatives of diols to 2-hydroxy ketones employing dioxiranes

1996 ◽  
Vol 37 (1) ◽  
pp. 115-118 ◽  
Author(s):  
Ruggero Curci ◽  
Lucia D'Accolti ◽  
Anna Dinoi ◽  
Caterina Fusco ◽  
Angela Rosa
Keyword(s):  
Selective Oxidation ◽  
Hydroxy Ketones ◽  
Isopropylidene Derivatives ◽  
Derivatives Of

Synthesis and Identification of ω-Phenylalkylcatechols in Burmese Lac

1988 ◽  
Vol 41 (1) ◽  
pp. 19 ◽  
Author(s):  
A Jefferson ◽  
MV Sargent ◽  
S Wangchareontrakul
Keyword(s):  
Natural Products ◽  
Catalytic Hydrogenation ◽  
Wittig Reaction ◽  
Spectral Characteristics ◽  
Chromatographic Retention ◽  
Phosphonium Bromide ◽  
Mass Spectral ◽  
Trimethylsilyl Derivatives ◽  
Derivatives Of

The presence of 3-(10′-phenyldecyl)-(2) (2%), 3-(12′-phenyldodecyl)- (3) (6%), 4-(10′-phenyldecyl)-(4) (0.3%) and 4-(12′-phenyldodecyl)- benzene-1,2-diol (5) (0.3%) in Burmese lac , the sap of Melanorrhoea usitata Wall has been confirmed by the synthesis of these compounds and a comparison of the gas chromatographic retention times and the mass spectral characteristics of their bis-O-( trimethylsilyl ) derivatives with the derivatives of the natural products. Typically, 3,4- bis ( benzyloxy ) benzaldehyde (7) on Wittig reaction with triphenyl (11- phenylundecyl ) phosphonium bromide (20) and subsequent catalytic hydrogenation of the resultant olefin gave compound (5) in 59% overall yield.

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