Water and methanol adsorption isotherms at 25° and 37° C.
were determined on a series of organo-bentonite clays. The clays
differed in the length of the carbon chain attached to the amine adsorbed
in the cation exchange position. The amines used had carbon
chains of 4, 6, 8, 10, 12,...
Part 1
The pyrolysis of cis-1-trimethylsiloxy-1-cyclopr opyl-3-cyclononene in the temperature range 285-350° is described. Instead
of siloxy-Cope rearrangement, undesired desiloxylation took place.
Part 2
Gas-phase pyrolytic rearrangement of 2-phenyl-1-trimethylsiloxy-1-vinylcyclononane was investigated in a static system
in the temperature range 213-330°. It was discovered that
three major products resulted: cis- and...
Both oxy-Cope and siloxy-Cope rearrangements involve
(1, 3) and (3, 3) sigrnatropic shifts. Both the concerted mechanism,
and the stepwise mechanism via a diradical intermediate are possible.
In a cyclic system such as cis-l-vinylcyclooct-3-en-l-ol, the thermal
rearrangement takes place preferably through a diradical intermediate.
At high temperature, the reaction also...
Six organoclay complexes have been studied in terms of their
selective adsorption from binary solutions of methanol and toluene.
Analyses are based on differential refractometry methods. The
isotherms were of the usual "S" type. The crossover points reveal
trends in the organophilic nature of the interlaminar surfaces in
these clay...
Part I
The pyrolysis of cis- and trans- 1, 2-divinyl-1- trimethylsiloxy -
cyclohexane, II- and III-TMS, under the same conditions as the
pyrolysis of cis-l-vinyl -1-trimethylsiloxycyclooct-3-ene, I-TMS,
confirms that a sequence of concerted reactions for the rearrangement
of II- and III-TMS to trans-l-trimethylsiloxycyclodec-3-ene,
IV-TMS, is a viable pathway in the...
The thermolysis of trans-1 -trimethylsiloxy- 1-vinylcyclotridec-
3-ene (VI-OTMS) led to the formation of two major products: 4-vinylcyclotridecanone
(VII) and cyclopentadec-5-en-l-one (VIII) after
hydrolysis. Ketone VII is produced by a concerted [3, 3] sigmatropic
shift, while ketone VIII is formed by a [1, 3] sigmatropic shift with
a concerted or diradical...
The reaction of cyclodeca-1,215triene with mercuric salts
gave only rearranged hydrocarbon, tricyclo[4.4.0.0²'⁴]deca-5ene
in acetic acid. Other catalysts [Rh(CO)₂C1]₂ and AgC10₄ gave
the same rearranged hydrocarbon. The isomerization is proposed
to proceed through a "metalcomplexed" carbenoid intermediate.
The reaction of bicyclo[7.1.0 ]deca-213diene gave
oxymercurated products.