US 4,233,230 AGranted

Process for preparing olefins by metathesis of cyclic olefins with acyclic olefins

AssigneeRhone-Poulenc Industries

InventorJean Otton

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Abstract

A process for preparing esters and halides is disclosed comprising the step of reacting a cyclic olefin having the formula I ##STR1## wherein R.sub.1 and R.sub.4 are the same or different from each other and each represents hydrogen, methyl, or ethyl; R.sub.2 and R.sub.3 are the same or different from each other and each represents hydrogen or alkyl containing 1 to 5 carbon atoms; and n represents a whole number from 2 to 12, with an acyclic olefin having the formula II ##STR2## wherein R.sub.5 represents hydrogen, methyl, ethyl or the group ##STR3## wherein R.sub.12 and R.sub.13 are the same or different from each other and each represents hydrogen or alkyl containing 1 to 5 carbon atoms; Y represents halogen; an acyloxy group R.sub.14 --CO--O wherein R.sub.14 represents alkyl containing 1-12 carbon atoms, phenyl or phenyl alkyl containing 7-12 carbon atoms, or an oxycarbonyl group R.sub.15 --O--CO wherein R.sub.15 represents alkyl containing 1-12 carbon atoms, phenyl or phenyl alkyl containing 7-12 carbon atoms; p represents a whole number from 1-12 except when Y is an R.sub.14 CO--O group wherein p is from 2 to 12. R.sub.6 and R.sub.7 are the same or different from each other and each represents hydrogen, methyl, or ethyl; R.sub.8 and R.sub.9 are the same or different from each other and each represents hydrogen or alkyl containing 1 to 5 carbon atoms; X represents halogen; an acyloxy group R.sub.10 --CO--O--, wherein R.sub.10 represents alkyl containing 1-12 carbon atoms, phenyl, or phenylalkyl containing 7-12 carbon atoms, or an oxycarbonyl group R.sub.11 --O--CO, wherein R.sub.11 represents alkyl containing 1-12 carbon atoms, phenyl, or phenylalkyl containing 7-12 carbon atoms, m represents a whole number from 1-12 except when X is an R.sub.10 --CO--O-- group wherein m is from 2 to 12 in the presence of a catalytic composition comprising a halogen-tungsten salt and a reducing agent which is an organic tin compound.

Claims22

Dependent claims

A process for preparing olefins which comprises, successively, the steps of:

(a) first introducing into a reactor (i) a cyclic olefin of formula I:
##STR21## wherein n represents a whole number from 2 to 12, and an acyclic olefin in an amount sufficient to achieve a molar ratio of cyclic to acyclic olefins of from about 0.5 to about 2.0, said acyclic olefin being of formula II:
##STR22## wherein R.sub.5 represents hydrogen, methyl, ethyl or the group:
##STR23## wherein R.sub.12 and R.sub.13 are the same or different from each other and each represents hydrogen or alkyl containing 1 to 5 carbon atoms;
Y represents halogen;
an acyloxy group R.sub.14 --CO--O-- wherein R.sub.14 represents alkyl containing 1 to 12 carbon atoms, phenyl or phenylalkyl containing 7 to 12 carbon atoms, or an oxycarbonyl group R.sub.15 --O--CO--, wherein R.sub.15 represents alkyl containing 1 to 12 carbon atoms, phenyl or phenylalkyl containing 7 to 12 carbon atoms;
p represents a whole number from 1 to 12 except when Y is an acyloxy group R.sub.14 --CO--O-- wherein P is from 2 to 12;
R.sub.6 and R.sub.7 are the same or different from each other and each represents hydrogen methyl or ethyl;
R.sub.8 and R.sub.9 are the same or different from each other and each represents hydrogen or alkyl containing 1 to 5 carbon atoms;
X represents halogen;
an acyloxy group R.sub.10 --CO--O--wherein R.sub.10 represents alkyl containing 1 to 12 carbon atoms, phenyl or phenyl alkyl, containing 7 to 12 carbon atoms;
or an oxycarbonyl group R.sub.11 --O--CO, wherein R.sub.11 represents alkyl containing 1 to 12 carbon atoms, phenyl or phenyl alkyl, containing 7 to 12 carbon atoms;
m represents a whole number from 1 to 12 except when X is an acyloxy group R.sub.10 --CO--O wherein m is from 2 to 12, and optionally (ii) a suitable solvent;
(b) then introducing into the reactor (i) a solution or suspension of a tungsten oxide salt wherein all or part of the oxygen atoms are replaced by halogen when the solvent is omitted from step (a), and (ii) said tungsten oxide salt being optionally in solid form when a solvent is present in step (a);
(c) after the reaction mixture from step (b) has become a homogeneous solution, adding thereto an organic-tin compound reducing agent and reacting said cyclic and acyclic olefins at a suitable temperature between about -20 and about 300.degree. C.;
and
(d) recovering a compound of formula III:
##STR24## wherein R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9, n, m, and X are as defined above.

15 more elements

A process for preparing olefins which comprises, successively, the steps of:

(a) first introducing into a reactor (i) a cyclic olefin from the group consisting of cyclobutene, cyclopentene, cycloheptene, cyclooctene, cyclodecene, and cyclododecene;
and an acyclic olefin in an amount sufficient to achieve a molar ratio of cyclic to acyclic olefin of from about 0.5 to about 2.0, said acyclic olefin being selected from the group consisting of methylbutene-3-oate, ethylbutene-3-oate, methylpentene-4-oate, ethylpentene-4-oate, methylpentene-3-oate, ethylpentene-3-oate, methylhexene-5-oate, ethylhexene-5-oate, 4-acetoxybutene-1,5-acetoxypentene-1, 6-acetoxyhexene-1, 4-benzoyloxybutene-1, benzylbutene-3-oate, benzylpentene-3-oate, methyl-3,3-dimethylpentene-4-oate, 4-chlorobutene-1, 5-chloropentene-1, 6-chlorohexene-1, 4-bromobutene-1, 6-bromohexene-1, methyl or ethyl-hexen-3-dioate-1,6;
methyl or ethyl-octen-4-dioate-1,8;
methyl or ethyl-octen-3-dioate-1,8;
methyl or ethyl-decen-5-dioate-1,10;
1,6-diacetoxy-3-hexene;
1,8-diacetoxy-3 or 4 octene;
and 1,10-diacetoxy-3 or 4 or 5 decene and optionally (ii) a suitable solvent;
(b) then introducing into the reactor (i) a solution or suspension of a tungsten oxide salt wherein all or part of the oxygen atoms are replaced by halogen selected from the group consisting of WCl.sub.6, WOCl.sub.4 WBr.sub.6, WOBr.sub.4, and WF.sub.6 when a solvent is omitted from step (a) and (ii) said tungsten oxide salt being optionally in solid form when a solvent is employed in step (a);
(c) after the reaction mixture from step (b) has become a homogeneous solution, adding thereto an organic tin compound reducing agent of the formula Sn(R).sub.4 wherein R represents alkyl and reacting said cyclic and acyclic olefins at a suitable temperature between about -20.degree. and about 300.degree. C.;
and
(d) recovering the metathesis reaction product of said cyclic and acyclic olefins.

9 more elements

Dependencies are inferred from the claim text.