TETRAHYDROFURANS: II. SPIRO COMPOUNDS CONTAINING THE TETRAHYDROFURAN RING

1963 ◽  
Vol 41 (12) ◽  
pp. 3070-3073
Author(s):  
B. K. Wasson ◽  
J. A. Kernan ◽  
J. M. Parker
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Mineral Acid ◽  
Spiro Compounds ◽  
Lithium Aluminum ◽  
Spectral Analyses ◽  
Nuclear Magnetic

2-Allyl-2-methallyl-1,3-propanediol (IV) and 2,2-dimethallyl-1,3-propanediol (V) were cyclized in the presence of mineral acid to give 3,3,8-trimethyl-2,7-dioxaspiro(4.4)nonane (VIII) and 3,3,8,8-tetramethyl-2,7-dioxaspiro(4.4)nonane (IX), respectively. Similarly, 2-methallyl-2-(3-methyl-2-butenyl)-1,3-propanediol (VI) afforded 3,3,8,8-tetramethyl-2,7-dioxaspiro(4.5)decane (X). The diol VI was derived from diethyl methallylmalonate by condensation with 3-methyl-2-butenyl bromide, followed by reduction of diethyl methallyl(3-methyl-2-butenyl)malonate (III) with lithium aluminum hydride. The assigned structures of the spiro compounds were supported by infrared and nuclear magnetic resonance spectral analyses.

scholarly journals Pyranosiduloses. II. The synthesis and properties of some alkyl 2,3-dideoxy-2-enopyranosid-4-uloses

1970 ◽  
Vol 48 (18) ◽  
pp. 2877-2884 ◽  
Author(s):  
Bert Fraser–Reid ◽  
Angus McLean ◽  
E. W. Usherwood ◽  
Mark Yunker
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Double Bond ◽  
Magnetic Resonance ◽  
Boron Trifluoride ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Lithium Aluminum ◽  
Crystalline Substance ◽  
Unsaturated Ketones ◽  
Olefinic Double Bond

Ethyl 2,3-dideoxy-α-D-erythro-hex-2-enopyranoside (9a) an accessible and highly crystalline substance is selectively oxidized at the allylic position to ethyl 2,3-dideoxy-α-D-glycero-hex-2-enopyranosid-4-ulose (10a) in 80% yield. This hydroxyketone can be benzoylated, acetylated, and tosylated, and the resulting esters are all highly crystalline, as is the parent ketone. 3,4-Di-O-acetyl-D-xylal reacts with ethanol under boron trifluoride catalysis to give the anomeric mixture of ethyl 4-O-acetyl 2,3-dideoxy-D-glycero-pent-2-enopyranosides which may be separated after deacetylation. The deacetylated α-D anomer (14α) is readily oxidized by manganese dioxide to give an ethyl 2,3-dideoxy pent-2-enopyranosid-4-ulose (6-ethoxy-2,6-dihydropyran-3-one) (12); however, the corresponding β-D (14β) anomer resists oxidation. All of these ketones display a diagnostic nuclear magnetic resonance pattern consisting of clean doublets for H-1 and -3, and a doublet of doublets for H-2. Reduction of 10a with lithium aluminum hydride gives back the parent D-erythro alcohol exclusively, and catalytic hydrogenation saturates the olefinic double bond. These α,β-unsaturated ketones (10) in the hexose series are all levorotatory although their parent D-erythro alcohols (9) are strongly dextrorotatory; the saturated ketones derived from them are also strongly dextrorotatory. The epimeric D-threo alcohols which should also be oxidizable to 10 are however strongly levorotatory.

Preparation and Spectral Analysis of 3,3',4,4'-Tetrachloroazobenzene and the Corresponding Azoxy and Hydrazo Analogs

1979 ◽  
Vol 62 (4) ◽  
pp. 746-750
Author(s):  
M T Stephen Hsia ◽  
Charles F Burant
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Chromatographic Method ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Lithium Aluminum ◽  
Reverse Phase ◽  
High Pressure Liquid Chromatographic ◽  
Hydride Reduction ◽  
Liquid Chromatographic Method ◽  
Liquid Chromatographic

Abstract An efficient preparation was developed for 3,3',4,4'-tetrachloroazobenzene and the corresponding azoxy and hydrazo derivatives, based on the lithium aluminum hydride reduction of 3,4-dichIoronitrobenzene. Batches were analyzed for purity by using a reverse phase high pressure liquid chromatographic method. All 3 compounds can be synthesized in gram quantities with 97–99% purity. Detailed mass, infrared, and nuclear magnetic resonance spectral analyses are presented.

Nuclear magnetic resonance spectral analyses of isothiazoles

1964 ◽  
Vol 1 (5) ◽  
pp. 279-279 ◽  
Author(s):  
Richard C. Anderson
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Spectral Analyses ◽  
Nuclear Magnetic

REPLACEMENT REACTIONS IN THE QUINIC ACID SERIES

1963 ◽  
Vol 41 (10) ◽  
pp. 2417-2423 ◽  
Author(s):  
P. A. J. Gorin
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Acetic Acid ◽  
Magnetic Resonance ◽  
Quinic Acid ◽  
Mineral Acid ◽  
Aqueous Acetic Acid ◽  
Nuclear Magnetic

The action on D-quinic acid of hot 95% acetic acid containing mineral acid gave, after complete acetylation, 1,4,5-tri-O-acetyl-epi-quinide consisting of approximately equal portions of the (−)- and (±)-isomers, and tetra-O-acetyl-scyllo-quinic acid. The stereochemistry of the products and their derived free polyols were determined by nuclear magnetic resonance (n.m.r.) spectroscopy and synthesis.Elimination of the tosyloxy group in 5-tosyl-epi-quinicol was shown to take place readily in aqueous acetic acid with participation of the primary carbinol group to give an anhydro quinicol derivative and epi-quinicol.

THE STRUCTURE OF MITRAPHYLLINE

1958 ◽  
Vol 36 (7) ◽  
pp. 1031-1038 ◽  
Author(s):  
J. C. Seaton ◽  
R. Tondeur ◽  
Léo Marion
Keyword(s):  
Double Bond ◽  
Experimental Evidence ◽  
Aromatic Amine ◽  
Lithium Aluminum Hydride ◽  
Aluminum Hydride ◽  
Mineral Acid ◽  
Lithium Aluminum ◽  
Spectroscopic Evidence ◽  
Mild Conditions ◽  
Total Structure

Mitraphylline (C21H24O4N2) contains a carbomethoxyl group, and on hydrolysis gives rise to mitraphyllic acid. Spectroscopic evidence shows that the alkaloid contains two chromophores, one characteristic of an oxindole and one corresponding to the grouping CH3OOC—Ć==CH.OR. On treatment with dilute mineral acid the alkaloid gives rise to mitraphyllal (C19H24O3N2), which is a hemiacetal that no longer contains the isolated double bond and the carbomethoxyl group originally present in the alkaloid. Reduction of mitraphyllal by the Wolff–Kishner reaction gives mitraphyllane (C19H26O2N2). The dehydrogenation of mitraphyllal produced 3,4-diethylpyridine and 3-ethyloxindole. The action of lithium aluminum hydride on mitraphylline under mild conditions gave rise to mitraphyllol by reduction of the carbomethoxyl group, and under more vigorous conditions to dihydrodesoxy-mitraphyllol by reduction of the oxindole carbonyl as well. This last product has the properties of an aromatic amine. On the basis of the new experimental evidence, a total structure of mitraphylline is derived.

TETRAHYDROFURANS: I. 2,2-DIMETHYL-4-SUBSTITUTED-4-HYDROXYMETHYLTETRAHYDROFURANS AND RELATED COMPOUNDS

1961 ◽  
Vol 39 (4) ◽  
pp. 923-932 ◽  
Author(s):  
B. K. Wasson ◽  
C. H. Gleason ◽  
I. Levi ◽  
J. M. Parker ◽  
L. M. Thompson ◽  
...  
Keyword(s):  
Acetic Anhydride ◽  
Pharmacological Activity ◽  
Lithium Aluminum Hydride ◽  
Catalytic Reduction ◽  
Aluminum Hydride ◽  
Mineral Acid ◽  
Lithium Aluminum ◽  
Pyridine Hydrochloride ◽  
Cyclic Compounds ◽  
Related Compounds

Substituted methallylmalonic esters (I) were reduced with lithium aluminum hydride to the corresponding 2-methallyl-1,3-propanediols (II). These diols II underwent cyclization on treatment with a mineral acid to the isomeric 2,2-dimethyl-4-substituted-4-hydroxymethyltetrahydrofurans (IV). II and IV were converted to the respective carbamates III and V, which exhibited pharmacological activity. The assigned structures of the cyclic compounds IV were proved by infrared analyses and the following transformations. Ring scission of 2,2-dimethyl-4-allyl-4-hydroxymethyltetrahydrofuran (IVe) with acetic anhydride – pyridine hydrochloride yielded 2-allyl-2-methallyl-1,3-propanediol diacetate (Xe). Catalytic reduction of IVe gave 2,2-dimethyl-4-n-propyl-4-hydroxymethyltetrahydrofuran (IVd). Reductive cleavage of the tosylate VIIIb of 2,2,4-trimethyl-4-hydroxymethyltetrahydrofuran (IVb) with lithium aluminum hydride yielded the known 2,2,4,4-tetramethyltetrahydrofuran (IXb).

scholarly journals Biocatalytic Synthesis of Vanillin

2000 ◽  
Vol 66 (2) ◽  
pp. 684-687 ◽  
Author(s):  
Tao Li ◽  
John P. N. Rosazza
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Carboxylic Acid ◽  
Magnetic Resonance ◽  
Vanillic Acid ◽  
Vanillyl Alcohol ◽  
Spectral Analyses ◽  
Enzyme Preparations ◽  
Mass Spectral ◽  
Whole Cells ◽  
Nuclear Magnetic

ABSTRACT The conversions of vanillic acid and O-benzylvanillic acid to vanillin were examined by using whole cells and enzyme preparations of Nocardia sp. strain NRRL 5646. With growing cultures, vanillic acid was decarboxylated (69% yield) to guaiacol and reduced (11% yield) to vanillyl alcohol. In restingNocardia cells in buffer, 4-O-benzylvanillic acid was converted to the corresponding alcohol product without decarboxylation. PurifiedNocardia carboxylic acid reductase, an ATP and NADPH-dependent enzyme, quantitatively reduced vanillic acid to vanillin. Structures of metabolites were established by 1H nuclear magnetic resonance and mass spectral analyses.

Derivatives of 2-pyrazolin-5-one. V. Preparation and properties of 1′,2′-dihydrospiro[[2]pyrazoline-4,3′ (4′H)-quinoline]-5-one.derivatives and related compounds

1977 ◽  
Vol 55 (15) ◽  
pp. 2856-2866 ◽  
Author(s):  
Ronald T. Coutts ◽  
Abdel-Monaem El-Hawari
Keyword(s):  
Acetic Acid ◽  
Sodium Borohydride ◽  
Lithium Aluminum Hydride ◽  
Catalytic Reduction ◽  
Aluminum Hydride ◽  
Spiro Compounds ◽  
Lithium Aluminum ◽  
Aldehydes And Ketones ◽  
Derivatives Of ◽  
Related Compounds

1′,2′-Dihydro-3-methyl-1-phenylspiro[[2]pyrazoline-4,3′(4′H)-quinoline]-5-one (8q), the structurally related 1,3-diphenylspiro[pyrazolone-quinoline] 8r and numerous 2′-substituted derivatives of 8q and 8r are readily accessible from catalytic reduction of 3-methyl-1-phenyl- or 1,3-diphenyl-4-(2-nitrobenzyl)-2-pyrazolin-5-one (1a, 1b, respectively) in alcohols (with the incorporation of the alkylidene moiety) or by interaction of the corresponding 2-aminobenzyl precursors (3a, 3b) with appropriate aldehydes and ketones. All spiro compounds were characterized by mass, ir, and 1Hmr spectra. The products obtained by reducing the spiro compounds with sodium borohydride and with lithium aluminum hydride are described. Reduction of 1a and 1b with zinc and acetic acid gave 3-methyl-1-phenyl- and 1,3-diphenyl-1H-pyrazolo[3,4-b]quinoline (2a, 2b, respectively).

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