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X in C4HB,Dx or C4HIo7Dx % Composition as given by GLC analysis. 58 46 %4 Fig. 18. The effect of mercury coverage ( 6 ~upon ~ ) t h e rates of hydrogenation olefin exchange (@) and isomerisation ( 8 ) of but-l-ene over r h o d i u m s i l i c a at 4 [129]. um at low temperatures (see Fig. 16 and ref. O, observed with the other noble Group VIII metals, may be explained by supposing that the conformations of the adsorbed but-2-yl group immediately before H-atom abstraction are important [ 1311. In an attempt t o understand further the mechanism of double bond migration, the reaction of but-l-ene with deuterium over mercury-poisoned rhodiumsilica catalysts was investigated [ 1291.

The preferential formation of cis-but-2-ene from but-1-ene, particularly noticeable with rhodi- -3 ; n 1 b P ," 4 1 TABLE 12 Product distributions from the reaction of the n-butenes with deuterium over palladiumalumina catalysts [ 1241 )-r 2 (J'R)o = (Pc~H&o = 60 torr _____________~~_ Reactant Conversion -- Temp. 0 36 a 2 a No species above - d ~were observed. x in C4HB,Dx or C4HIo7Dx % Composition as given by GLC analysis. 58 46 %4 Fig. 18. The effect of mercury coverage ( 6 ~upon ~ ) t h e rates of hydrogenation olefin exchange (@) and isomerisation ( 8 ) of but-l-ene over r h o d i u m s i l i c a at 4 [129].

Butane (%) 0 50 n -Butane 100 (O/d Fig. 1 6 . Distribution o f t h e n-butenes as a function of t h e extent of hydrogenation of but-l-ene a t 25OC over (a) rhodium-alumina and (b) r h o d i u m s i l i c a [ 1 2 5 ] . 0 , But-1ene; 3,t r a n s - b u t - l e n e ; f cis-but-2-ene. References p p . 0 ? 1 a ? 08 0 Catalyst Olefin Temp. o 0 0 ~~ Valid at low pressure; as P,, increased, m decreased. 4 Ref. 05 ? 4 124 103 43 The second method, derived by Hamilton and Burwell El271 for the hydroisomerisation of cis-but-2-ene over palladiumalumina, requires the assumption that the isomerisation and hydrogenation reactions have identical kinetic form and that the rates of hydrogenation of the butenes are identical.

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Aromatic Substitution Products with Fluorine by Bancroft W. D.


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