Solvolysis of Substituted Nortricyclanes and Norbornenes at 250°

tetralin (16) have been labelled with deuterium by the high temperature -dilute acid (HTDA) method. In dilute DCl/D20 (0.14-0.27 M) at temperatures of 250-285"C, the ring hydrogens of these compounds equilibrate with the deuterium pool. At temperatures above 250°C the methyl groups of 3, 4, 5, 6 and 11 undergo slow HID exchange; the methyl groups of 8, 9, 10, and 13 undergo exchange much more readily and hexamethylbenzene (13) can be readily perlabelled. Hexamethylbenzene exhibits a lower reactivity than 13 at the benzylic sites.

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Protium–deuterium exchange of alkylated benzenes in dilute acid at elevated temperatures

Timmins¹

1989

“…Under similar condiInitial studies of the application of high temperature -dilute tions in deuteriated medium (entry 21, l a incorporates 6.03 D acid (HTDA) exchange have established that a wide range of atoms Per molecule (0.4% do, 0.5% dl 0.7% d2, 1.2% d3, aromatic compounds can be specifically labelled or perlabelled 3.5% d4, 15.2% d5, 57.0% d69 11.5% d7, 6.9% ds, 2.7% d9, (1)(2)(3)(4)(5)(6)8). In continuing these studies, we examined a series and 0.5% dlo species).…”

Section: Introductionmentioning

confidence: 99%

H–D exchange of 1-methylcycloalkenes in dilute acid at elevated temperatures

Timmins¹

1986

Specifically deuteriated cycloalkenes 1-trideuteriomethylcyclopentene-2,5,5-d6 (1b), 1-trideuteriomethylcyclohexene-2,6,6-d6(2b), 1-trideuteriomethylcycloheptene-2,7,7-d6 (3b), and 1-trideuteriomethylcyclooctene-2,8,8-d6 (4b) have been prepared from the corresponding protiated substrates 1a, 2a, 3a, and 4a using a modified HTDA exchange method. The perlabelled analogues of 1a and 2a, 5 and 6, have been synthesized by the same method.

“…solvolysis and hydration of organic molecules in dilute aqueous acid (1,9) at moderately high temperatures (>_250°C), we have studied the reaction of norbornadiene and benzonorbornadiene in deuterated and non-deuterated media under high temperature -dilute acid (HTDA) conditions.…”

Section: H20 Onlymentioning

confidence: 99%

Reaction of organic compounds under high temperature – dilute acid (HTDA) conditions. II. The hydration–exchange of norbornadiene and benzonorbornadiene in aqueous acetic acid at 250 °C

Kadai¹

1976

The hydration of norbornadiene (1) under the HTDA conditions of aqueous acetic acid at 250 °C gives via norbornanediols and norbornenols as intermediates, the sink-product aldehydes 3, 4, 5, and norcamphor (6). When the reaction is carried out in deuterated medium on the average, 2.5 atoms of deuterium are incorporated into each of the products. Hydration of benzonorbornadiene (2) at 250 °C gives the alcohols 40 and 41 and the acetates 42a and 42b as products. When the hydration is carried out in deuterated medium, while only one atom of deuterium is incorporated into the [2.2.1]-framework, exchange of the aromatic moiety proceeds to completion.