Kinetic study of chlorine-isotopic exchange between lithium chloride and di- and tri-nitro-derivatives of m- and p-dichlorobenzenes

Journal Article · Mon Jan 01 04:00:00 EST 1973 · J. Chem. Soc., Perkin Trans., II, no. 14, pp. 1883-1887

DOI:https://doi.org/10.1039/p29730001883· OSTI ID:4410536

Gore, P H; Hammond, S D; Morris, D F.C.

>The kinetics of chlorine isotopic exchange between di- or trinitro- derivatives of m- or p-dichlorobenzene with Li/sup 36/Cl were measured. Second- order rate constants for 1,3-dichloro-4,6dinitrobenzene increase in the sequence of solvents; isopropyl alcohol << acetylacetone < sulpholan < dimethyl sulphoxide < 97: 3 (v/v) diethyl ketone-n-butanol < acetone < hexamethylphosphoramide < diethyl ketone. No exchange was observed for dioxan or glacial acetic acid solutions. Water exerts a strong retarding effect on the rate of exchange of this substrate in acetone solution. Rate-constants relative to 1-chloro-2,4- dinitrobenzene = 1.00, at 298 deg K in anhydrous acetone solution were: 1,3- dichloro2,4-dinitrobenzene 0.019, 1,4-dichloro-2,6-dinitrobenzene 0.61, 1,3- dichloro-4,6-dinitrobenzene 26, and 1,3-dichloro-2,4,6trinitmbenzene 32,000. With 1,3-dichloro-2,4-dinitro- and 1,4dichloro-2,6-dinitrobenzene only the 1- chloro-groups undergo exchange, under the conditions used. (auth) rogen at C/sub BETA / enables determination of primary kinetic isotope effects k/sub H/k/ sub D/ for eliminat ion and secondardy isotope effects for substitution of alkyl halides and sulfonates. (LK)

• Research Organization: Univ. of Brunel, London
• NSA Number: NSA-29-009889
• OSTI ID: 4410536
• Journal Information: J. Chem. Soc., Perkin Trans., II, no. 14, pp. 1883-1887, Journal Name: J. Chem. Soc., Perkin Trans., II, no. 14, pp. 1883-1887; ISSN JCPKB
• Country of Publication: United Kingdom
• Language: English

Related Subjects

*CHLORINE 36-- ISOTOPIC EXCHANGE
ACETIC ACID
ACETONE
ACETYLACETONE
AMIDES
AROMATICS
ARRHENIUS EQUATION
BUTANOLS
CHEMICAL REACTION KINETICS
DIOXANE
DMSO
LABELLED COMPOUNDS
LITHIUM CHLORIDES
N40220* --Chemistry--Inorganic
Organic
&amp; Physical Chemistry--Isotopic Effects
NITRO COMPOUNDS
ORGANIC CHLORINE COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
SOLVENTS
WATER