scholarly journals Rearrangements in the acid-catalyzed formation of lactones from 2-hydroxynorbornane-2-acetic acid derivatives and related compounds

1992 ◽  
Vol 70 (9) ◽  
pp. 2491-2501 ◽  
Author(s):  
Peter Yates ◽  
Magdy Kaldas
Keyword(s):  
Acetic Acid ◽  
Sulfuric Acid ◽  
Ethyl Esters ◽  
Alkyl Groups ◽  
Acid Lactone ◽  
Concentrated Sulfuric Acid ◽  
Acid Catalyzed ◽  
Preliminary Study ◽  
Related Compounds ◽  
Acetic Acids

A mixture of the epimeric ethyl 2-hydroxynorbornane-2-acetates (1) on treatment with concentrated sulfuric acid is converted in turn to the lactones of exo-2-hydroxynorbornane-1-acetic acid (4), endo-6-hydroxynorbornane-endo-2-acetic acid (5), and exo-3-hydroxynorbornane-exo-2-acetic acid (6). With trifluoroacetic acid or 50% sulfuric acid, 1 gives 4, but this does not react further. In concentrated sulfuric acid the parent acids of 1 (7) and (E)- and (Z)-(norborn-2-ylidene)acetic acids (8 and 9) and their ethyl esters (10 and 11) give 6 as the infinity product. A mixture of 5-norbornene-endo- and exo-2-acetic acid (30 and 31) on treatment with 50% sulfuric acid gives 4, 5, 6, and exo-2-hydroxynorbornane-syn-7-acetic acid lactone (33). Routes are proposed for the formation of the lactones that involve protonation and carbocation formation followed by rearrangement via Wagner–Meerwein, endo-6,2-hydride, and exo-3,2-hydride shifts in decreasing order of preference. It is postulated that the usual inhibition of the rearrangement of tertiary to secondary norbornyl carbocations is not operative when the third substituent is a carboxymethyl group or its derivatives because of the electron-withdrawing properties of such groups relative to simple alkyl groups. A preliminary study has shown that exo-5-acetyloxy-endo-2-hydroxynorbornane-exo-2-acetic acid (35) with 50% sulfuric acid gives four products that are considered to be the γ-lactones of endo-5-acetyloxy- and endo-5-hydroxynorbornane-1-acetic acid (38 and 39) and exo-2-acetyloxy-1-hydroxy-and 1,2-dihydroxynorbornane-syn-7-acetic acid (40 and 41). Protonation of either the hydroxyl or acetyloxyl group is postulated, giving two carbocations that undergo rearrangements as in the case of 1, together with 3,2-hydroxyl shifts. The structures of the lactones are assigned on the basis of spectroscopy, reactivity, and analogy. The reactions of the lactones, which lead to a variety of hydroxy- and oxonorbornaneacetic acids, illustrate their synthetic potential.

Antiaminic agents derived from thieno[2,3-c]-2-benzothiepin: 4-(1-Methyl-4-piperidylidene)-4,9-dihydrothieno[2,3-c]-2-benzothiepin and some related compounds

1983 ◽  
Vol 48 (2) ◽  
pp. 623-641 ◽  
Author(s):  
Zdeněk Polívka ◽  
Miroslav Rajšner ◽  
Jan Metyš ◽  
Jiří Holubek ◽  
Emil Svátek ◽  
...  
Keyword(s):  
Clinical Trials ◽  
Sulfuric Acid ◽  
Title Compound ◽  
Amino Alcohol ◽  
Hydrogen Sulfate ◽  
Geometric Isomers ◽  
Pure Alcohol ◽  
Acid Catalyzed ◽  
Anticataleptic Activity ◽  
Related Compounds

In the reaction of thieno[2,3c]-2-benzothiepin-4(9H)-one (VI) with 1-methyl-4-piperidylmagnesium chloride 7-(1-methyl-4-piperidyl)thieno[2,3-c]-2-benzothiepin-4(9H)-one (VIII) is formed in addition to the expected amino alcohol VII. The title compound I was obtained by the acid catalyzed dehydration of the pure alcohol VII. Compound I (pipethiadene) has outstanding antihistamine, antiserotonin, antireserpine and anticataleptic activity and was recommended to clinical trials as a potential antimigraine agent. For pharmacokinetic and metabolic studies there were prepared the NC2H3 analogue of pipethiadene IV and further, as potential metabolites, the demethyl analogue III, S-oxide X, demethyl S-oxide XI, N-oxide XIII and N,S-dioxide XIV. The Witting reaction of the ketone VI with 3-dimethylaminopropylidenetriphenylphosphorane resulted in a mixture of geometric isomers of 4-(3-dimethylamino-propylidene)-4,9-dihydrothieno[2,3-c]-2-benzothiepin with the strongly predominating Z-isomer XVI which was isolated from the mixture by crystallization of the hydrogen maleate. The mixture with the predominating Z-isomer XVI was converted by the treatment with 80% sulfuric acid and dilution with water to a mixture with the predominating E-isomer XV (dithiadene) which was isolated by crystallization of the hydrogen sulfate. Some further new thieno[2,3-c]-2-benzothiepin derivatives were synthesized as potential intermediates.

The decomposition of aliphatic N-nitro amines in aqueous sulfuric acid. Bisulfate as a nucleophile

1996 ◽  
Vol 74 (10) ◽  
pp. 1774-1778 ◽  
Author(s):  
Robin A. Cox
Keyword(s):  
Sulfuric Acid ◽  
Water Molecule ◽  
Rate Constants ◽  
Activation Parameters ◽  
Standard State ◽  
Aqueous Sulfuric Acid ◽  
Alkyl Groups ◽  
Different Temperatures ◽  
State Rate ◽  
Acid Catalyzed

In aqueous sulfuric acid, aliphatic N-nitro amines decompose to N2O and alcohols. An excess acidity analysis of the observed rate constants for the reaction shows that free carbocations are not formed. The reaction is an acid-catalyzed SN2 displacement from the protonated aci-nitro tautomer, the nucleophile being a water molecule at acidities below 82–85% H2SO4, and a bisulfate ion at higher acidities. Bisulfate is the poorer nucleophile by a factor of about 1000. Twelve compounds were studied, of which results obtained for nine at several different temperatures enabled calculation of activation parameters for both nucleophiles. The reaction appears to be mainly enthalpy controlled. The intercept standard-state rate constants are well correlated by the σ* values for the alkyl groups; the slopes are negative, with a more negative value for the slower bisulfate reaction. Interestingly the m≠m* slopes also correlate with σ*, although the scatter is bad. Key words: N-nitro amines, excess acidity, bisulfate, nucleophiles, acid-catalyzed, kinetics.

Synthèse de quelques dérivés du tétrahydro-4,5,6,7 benzothiazoline-Δ2α-acétate d'éthyle

1968 ◽  
Vol 46 (23) ◽  
pp. 3643-3648 ◽  
Author(s):  
Réal Laliberté ◽  
Hilda Warwick ◽  
Georges Médawar
Keyword(s):  
Acetic Acid ◽  
Sulfuric Acid ◽  
Spectroscopic Evidence ◽  
Concentrated Sulfuric Acid ◽  
Derivatives Of

Some derivatives of α-cyano tétrahydro benzothiazoline-Δ2α-acetic acid and their intermediates are described. The lack of reactivity of this class of compounds and products of treatment with concentrated sulfuric acid have been studied. Assignment of configuration was based on infrared and ultraviolet spectroscopic evidence.

Cyclodiene Chemistry. III. Derivative Formation for the Identification of Heptachlor, Heptachlor Epoxide, cis-Chlordane, irans-Chlordane, Dieldrin, and Chromatography

1969 ◽  
Vol 52 (6) ◽  
pp. 1220-1226 ◽  
Author(s):  
Alfred S Y Chau ◽  
W P Cochrane
Keyword(s):  
Sulfuric Acid ◽  
Acid Treatment ◽  
Heptachlor Epoxide ◽  
Improved Method ◽  
Sulfuric Acid Treatment ◽  
Subsequent Conversion ◽  
Concentrated Sulfuric Acid ◽  
Acid Catalyzed ◽  
Cis And Trans ◽  
Feed Samples

Abstract An improved method, involving potassium tert.-butoxide and tert.-butanol treatment followed by acetylation, is described for the similtaneous confirmation of heptachlor, heptachlor epoxide, and cis- and trans-chlordanes in cleaned-up feed samples. Parent pesticide residues can be identified at levels of 0.01 ppm and above. As a confirmative test for dieldrin, the formation of an acetate and subsequent conversion to a “ketone” by acetic anhydride/ sulfuric acid treatment is used. The concentrated sulfuric acid-catalyzed isomerization of endrin is also reported.

Bromination of Acridine

2018 ◽  
Vol 71 (4) ◽  
pp. 285
Author(s):  
Graham S. Chandler ◽  
Wolfgang H. F. Sasse
Keyword(s):  
Acetic Acid ◽  
Sulfuric Acid ◽  
Quantitative Determination ◽  
Glacial Acetic Acid ◽  
Tiny Amount ◽  
Concentrated Sulfuric Acid

The quantitative determination of the products of bromination of acridine in concentrated sulfuric acid and glacial acetic acid is described. In both cases, the only monobromo products were the 2- and 4-substituted compounds. With sulfuric acid, the 4-isomer predominates whereas in acetic acid, the 2-isomer is predominant. This work expands substantially on the tiny amount of previous work on halogenation of dibenzo-annelated pyridines.

REACTIONS OF AMIDES AND RELATED COMPOUNDS: III. N.M.R. INVESTIGATION OF THE PROTONATION OF N,N-DIMETHYLNITROSOAMINE, N,N-DIETHYLNITROSOAMINE, AND N-NITROSOPIPERIDINE

1966 ◽  
Vol 44 (2) ◽  
pp. 105-109 ◽  
Author(s):  
Stephen J. Kuhn ◽  
John S. McIntyre
Keyword(s):  
Sulfuric Acid ◽  
Magnetic Resonance ◽  
Perchloric Acid ◽  
Trifluoroacetic Acid ◽  
Proton Magnetic Resonance ◽  
Acid Solutions ◽  
Concentrated Sulfuric Acid ◽  
Related Compounds ◽  
Equimolar Solution ◽  
Magnetic Resonance Spectra

Protonation of N,N-dimethylnitrosoamine has been investigated by dissolving the nitrosoamine in different acids and recording the proton magnetic resonance spectra of these solutions. Concentrated sulfuric acid, sulfuric acid monohydrate, perchloric acid (72%), trifluoroacetic acid, and fluorosulfuric acid have been used in this study. Only in fluorosulfuric acid near 0 °C and lower was a new signal observed for the protonated nitrosoamine molecule. Integration of the peaks has shown that only one proton is captured by the nitrosoamine. The following structure is suggested for the protonated nitrosoamine.[Formula: see text]The n.m.r. spectra of fluorosulfuric acid solutions of N,N-diethylnitrosoamine and N-nitrosopiperidine also show separate signals for the captured proton.The n.m.r. spectrum of an equimolar solution of N,N-dimethylnitrosoamine, N,N-dimethylformamide, and trifluoroacetic acid in 2-nitropropane indicates that N,N-dimethylnitrosoamine is a weaker base.

Acid-catalyzed rearrangement of 3-carene-2,5-dione (3,7,7-trimethylbicyclo[4.1.0]hept-3-ene-2,5-dione)

1970 ◽  
Vol 48 (6) ◽  
pp. 1013-1016 ◽  
Author(s):  
I. W. J. Still ◽  
G. W. Nathan
Keyword(s):  
Sulfuric Acid ◽  
Acetic Anhydride ◽  
Concentrated Sulfuric Acid ◽  
Acid Catalyzed

The reaction of 3-carene-2,5-dione (2) with acetic anhydride–concentrated sulfuric acid at 25° has been shown to lead exclusively to the formation of 2-methyl-6-isopropenylhydroquinone diacetate (3b).

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