Chemistry of hydrocarbon compounds – Unsaturated compound synthesis – By addition of entire unsaturated molecules – e.g.,...
Reexamination Certificate
2000-05-25
2002-05-14
Griffin, Walter D. (Department: 1764)
Chemistry of hydrocarbon compounds
Unsaturated compound synthesis
By addition of entire unsaturated molecules, e.g.,...
C585S513000, C585S329000, C585S664000
Reexamination Certificate
active
06388160
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method for producing 2,3-dimethylbutene-1 and 2,3-dimethylbutene-2, which are useful intermediate for the production of agrochemicals, medicine, aromatics, cosmetics and the like.
2. Description of Related Art
There has been known a method for producing 2,3-dimethylbutene-1 (hereinafter, referred to as DMB-1) and 2,3-dimethylbutene-2 (hereinafter, referred to as DMB-2) as disclosed in Japanese Patent No. 2577772. Since it has been difficult, as the patent disclosed, to separate DMB-1 of good purity from propylene-dimerization reaction mixture containing a considerable amount of several by-products such as 4-methylpentene-1, cis or trans-4-methylpentene-2 of which boiling points differ from that of DMB-1 by only 1 to 3° C., DMB-1 has been produced by thermodynamically unfavorable reverse isomerization reaction of isolated DMB-2, which was prepared by isomerization DMB-1 contained in a propylene-dimerization reaction mixture.
SUMMARY OF THE INVENTION
An object of the invention is to provide an efficient method for production of DMB-1 and DMB-2, which has been accomplished by using a nickel catalyst having good selectivity and one isomerization step instead of cumbersome two isomerization steps including thermodynamically unfavorable reverse isomerization.
The present invention provides:
a method for producing 2,3-dimethylbutene-1 and 2,3-dimethylbutene-2,
comprising the steps of
(a) dimerizing propylene in a propylene-dimerization step using a nickel complex catalyst as described below as a propylene-dimerization catalyst having propylene-dimerization activity and DMB-1 selectivity,
(b) rectifying the resulting reaction solution to obtain 2,3-dimethylbutene-1 as a distillate and a distillation residue containing 2,3-dimethylbutene-1 in a 2,3-dimethylbutene-1 distillation step,
(c) allowing the distillation residue to contact with sulfuric acid, sulfonic acid or hetetopolyacid to isomerize 2,3-dimethylbutene-1 in said distillation residue into 2,3-dimethylbutene-2 in an isomerization step, and
(d) rectifying the resulting isomerization reaction solution to obtain 2,3-dimethylbutene-2 in a 2,3-dimethylbutene-2 distillation step,
wherein said nickel complex catalyst comprising
(A) at least one nickel compound selected from a nickel salt of an organic or inorganic acid and a complex compound of nickel,
(B) a trialkylaluminum,
(C) a trivalent phosphorus compound of formula (1):
PR
1
R
2
R
3
(1)
wherein, R
1
, R
2
and R
3
are the same or different and represent a phenyl which may be substituted with an alkyl or alkoxy group, an alkyl group, a cycloalkyl group or an aralkyl group,
(D) a fluorinated isopropanol or a halogenated phenol of formula (2):
wherein X
1
to X
5
are the same or different and independently represent a halogen or hydrogen atom and at least one of X
1
to X
5
is a halogen atom, and
(E) at least one sulfur compound selected from a sulfonic acid and a dialkylsulfuric acid.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will be described in detail below.
Examples of the nickel compound as the propylene-dimerization catalyst component (A) used in the present invention include
an organic acid salt of nickel (e.g., (C1-C15)hydrocarbylcarboxylic acid such as nickel formate, nickel acetate and nickel naphthenate and the like),
an inorganic acid salt of nickel such as nickel chloride, nickel bromide, nickel nitrate and the like, and
a complex compound of nickel such as nickel bisacetyl acetonate and the like. These nickel compound can also be used in combination of two or more thereof.
Examples of the trialkylaluminum as the catalyst component (B) include tri(C1-C6) alkylaluminium such as trimethylaluminum, triethylaluminum, tri-n-propylaluminum, tri-n-butylaluminum, triisobutylaluminum, tri-n-pentylaluminum, tri-n-hexylaluminum and the like. The catalyst component (B) is used in an amount of usually about 2 to 500 moles, preferably about 2 to 100 moles per mol of the catalyst component (A).
Next, a description will be made to the trivalent phosphorus compound of formula (1).
Examples of the alkyl group on the phenyl group in R
1
, R
2
or R
3
include a (C1-C3)alkyl group such as a methyl, ethyl, n-propyl, I-propyl group.
Examples of the alkoxy group on the phenyl group in R
1
, R
2
and R
3
include a (C1-C3)alkoxy group such as a methoxy, ethoxy, n-propoxy or i-propoxy group.
Examples of the phenyl group which may be substituted with an alkyl or alkoxy group include a tolyl group, o-, m-, p-methoxyophenyl group.
Examples of the alkyl group for R
1
, R
2
and R
3
include a (C1-C6) alkyl such as a methyl, ethyl, isopropyl, t-butyl, sec-butyl, n-pentyl or n-hexyl group.
Examples of the cycloalkyl group for R
1
, R
2
and R
3
include a (C5-C6)cycloalkyl group such as a cyclopentyl or cyclohexyl group.
Examples of the aralkyl group include a (C7-C11)aralkyl group such as benzyl, phenylethyl, 1-, or 2-naphthylmethyl group.
Specific examples of the tri-valent phosphorus compound as the catalyst component (C) include triisopropylphosphine, tri-t-butylphosphine, tri-sec-butylphosphine, tricyclohexylphosphine, ethyl-di-t-butylphosphine, tri-o-tollylphosphine and the like. The catalyst component (C) is used in an amount of usually about 0.1 to 20 moles, preferably about 0.5 to 2 moles per mol of the catalyst component (A).
Examples of the fluorinated isopropanol as the catalyst component (D) include 1,1,3,3-tetrafluoroisopropanol, 1,1,1,3,3-pentafluoroisopropanol, 1,1,1,3,3,3-hexafluoroisopropanol and the like.
Examples of the halogenated phenols of formula (2) include o-, m-, p-chlorophenol, 2,3-, 2,4-, 2,6-, 3,4- and 3,5-dichlorophenol, 2,4,5- and 2,4,6-trichlorophenol, 2,3,4,6-tetrachlorophenol, pentachlorophenol and the like.
The amount of catalyst component (D) is usually about 0.4 to 20 moles, preferably about 1 to 10 moles per mol of the catalyst component (B).
Examples of the sulfonic acid selected as a sulfur compound as the catalyst component (E) include
an aliphatic sulfonic acid, (e.g., a (C1-C2)aliphatic sulfonic acid such as methanesulfonic acid, ethanesulfonic acid and the like),
an aromatic sulfonic acid such as benzenesulfonic acid, p-toluenesulfonic acid and the like having 6-7 carbon atoms, and
a halogen-containing sulfonic acid having up to 1 carbon atom such as chlorosulfonic acid, trifluoromethanesulfonic acid and the like.
Examples of the dialkylsulfuric acid include a di(C1-C2)alkylsulfuric acid such as dimethylsulfuric acid and diethylsulfuric acid. These can also be used in admixture of two or more thereof.
The amount of catalyst component (E) is usually about 0.1 to 10 moles per mol of the catalyst component (A).
The preparation of the catalyst is usually conducted in the presence of an inert solvent, and examples thereof include toluene, chlorobenzene, hexane, heptane, dichloroethane and the like. The mixing order of catalyst components is not particularly restricted, and the mixing of catalyst components is preferably conducted in the presence of a conjugated diene such as butadiene, isoprene and the like, and in this case, a catalyst having particularly good stability can be obtained. The conjugated diene is preferably used in an amount of about 1 to 200 moles per mol of the catalyst component (A).
The temperature for preparing the catalyst is usually from about −50 to 30° C. The propylene-dimerization reaction is conducted in an inert solvent such as toluene, chlorobenzene, hexane, heptane, dichloroethane. The concentration of the catalyst component in the reaction is usually from about 10
−5
to 10
−10
mol/l in terms of a nickel atom.
The reaction temperature is usually from about −20 to 50° C., the reaction time is usually from 30 minutes to 100 hours, and the pressures in the system is usually from 0 to 30 kg/cm
2
G.
Thus obtained propylene-dimerization reaction solution may be rectified as it is to obtain DMB-1, or the dimerization catalyst may be de-activated and removed before distill
Itagaki Makoto
Suzukamo Gohfu
Yamamoto Michio
Griffin Walter D.
Nguyen Tam M.
Sumitomo Chemical Company Limited
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