Organic compounds -- part of the class 532-570 series – Organic compounds – Carboxylic acid esters
Reexamination Certificate
2000-04-17
2001-10-09
Gitomer, Ralph (Department: 1623)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carboxylic acid esters
C560S244000, C560S246000, C560S262000
Reexamination Certificate
active
06300515
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for isomerizing a compound having an acyloxyl group or a hydroxyl group at the allylic position thereof. The present invention also relates to a process for isomerizing 3,4-disubstituted-1-butene and/or 1,4-disubstituted-2-butene using a specific catalyst to produce, respectively, the corresponding isomers, 1,4-disubstituted-2-butene and/or 3,4-disubstituted-1-butene.
2. Discussion of the Background
1,4-diacetoxy-2-butene is an important intermediate for producing 1,4-butanediol, tetrahydrofuran or the like. 3,4-diacetoxy-1-butene is an important intermediate for producing medicines, agricultural chemicals, various aromatics, terpentene compounds such as vitamin A acetate, and the like.
It is known that 1,4-diacetoxy-2-butene and 3,4-diacetoxy-1-butene may be obtained by oxidizing butadiene in an acetic acid solvent with molecular oxygen (e.g., Laid-Open Japanese Patent Application (JP-A) Nos. 48-72090, 48-96513). However, it is extremely difficult to produce 1,4-diacetoxy-2-butene and 3,4-diacetoxy-1-butene in an arbitrary ratio by this method, since the production ratio of 1,4-diacetoxy-2-butene to 3,4-diacetoxy-1-butene is influenced mainly by the ability of the catalyst.
Although 3,4-diacetoxy-1-butene is easily obtained by acetoxylating 1,2-epoxy-3-butene, it is extremely difficult to obtain 1,4-diacetoxy-2-butene by this method. On the other hand, extremely specific raw materials such as 3,6-dihydro-1,2-dioxine and the like are required for producing only 1,4-diacetoxy-2-butene selectively. Therefore, it is virtually impossible to produce 1,4-diacetoxy-2-butene on an industrial scale.
Accordingly, conventional methods for isomerizing 3,4-disubstituted-1-butene and/or 1,4-disubstituted-2-butene using a particular catalyst have been suggested to produce the corresponding respective isomers, 1,4-diacetoxy-2-butene and/or 3,4-diacetoxy-1-butene. These include, for example, a method using a platinum chloride compound as a catalyst (DE U.S. Pat. Nos. 2,736,695 and 2,134,115), a method using a palladium compound in combination with hydrogen chloride or hydrogen bromide (JP-A No. 57-140744), a method using a PdCl
2
(PhCN)
2
compound (U.S. Pat. No. 4,095,030) and the like. However, these methods use a halogen compound as a catalyst and have problems with the stability of the catalyst. These methods are undesirable industrially since they require large amounts of corrosive halogen compound.
Methods are known which avoid the use of halogen compounds, and these include a method using a catalyst composed of a palladium compound and an organic phosphine (JP-A No. 55-11555) and a method of conducting isomerization in a gas phase using an acid catalyst such as alumina, zeolite and the like (DE-Patent No. 3326668, JP-A No. 50-126611). However, these methods have problems in that either the activity of the catalyst is unsatisfactory or the selectivity of the catalyst is not sufficient and the like, and, accordingly, these methods are unsatisfactory from an industrial point of view.
As described above, 1,4-diacetoxy-2-butene and 3,4-diacetoxy-1-butene are intermediates for utterly different product groups, as noted above. Since each intermediate is useful in widely varying applications, the desired ratio, e.g., in a mixture of 1,4-diacetoxy-2-butene and 3,4-diacetoxy-1-butene depends greatly on area, era or business background of an enterprise carrying them out. Namely, it is extremely significant to isomerize 3,4-diacetoxy-1-butene and/or 1,4-diacetoxy-2-butene to produce the corresponding respective isomers, ,4-diacetoxy-2-butene and/or 3,4-diacetoxy-1-butene, according to industrial needs.
SUMMARY OF THE INVENTION
Accordingly, one object of the present invention is to provide a process for isomerizing allylic substrates having at the allyl position an acyloxyl group or a hydroxyl group to produce the respective corresponding allylic isomers and which avoids the aforementioned problems.
Another object of the present invention is to provide a process for isomerizing allylic substrates having at the allyl position an acyloxyl group or a hydroxyl group, such as 3,4-disubstituted-1-butene and/or 1,4-disubstituted-2-butene and the like.
Another object of the present invention is to provide a process for isomerizing allylic substrates having at the allyl position an acyloxyl group or a hydroxyl group, such as 3,4-disubstituted-1-butene and/or 1,4-disubstituted-2-butene and the like, to produce allylic compounds such as 1,4-disubstituted-2-butene and/or 3,4-disubstituted-1-butene and the like.
Another object of the present invention is to provide a process for isomerizing allylic substrates having at the allyl position an acyloxyl group or a hydroxyl group at a high conversion rate.
Another object of the present invention is to provide a process for isomerizing allylic substrates having at the allyl position an acyloxyl group or a hydroxyl group with high selectivity.
Another object of the present invention is to provide a process for isomerizing allylic substrates having at the allyl position an acyloxyl group or a hydroxyl group while suppressing the deposition of metals derived from isomerization catalyst compounds.
Another object of the present invention is to provide a process that contributes to the efficient production of 1,4-butylene glycol.
These and other objects have been achieved by the present invention, the several embodiments of which are summarized below.
Accordingly, one embodiment of the invention provides a process, that includes:
isomerizing at least one allylic substrate having an acyloxyl group or a hydroxyl group at the allyl position thereof, to produce a corresponding allylic isomer, wherein the isomerizing is conducted in the presence of a catalyst that includes a Group VIII-X metal compound and a phosphite compound.
Another embodiment of the present invention provides a process for isomerizing a mixture of 3,4-diacetoxy-1-butene and 1,4-diacetoxy-2-butene to produce a mixture of the corresponding allylic isomers, 1,4-diacetoxy-2-butene and 3,4-diacetoxy-1-butene, wherein the isomerization is conducted in the presence of a catalyst containing a Group VIII-X metal compound and a phosphite compound.
Another embodiment of the present invention provides a process for isomerizing 3,4-diacetoxy-1-butene to produce the corresponding allylic isomer, 1,4-diacetoxy-2-butene, wherein the isomerization is conducted in the presence of a catalyst containing a Group VIII-X metal compound and a phosphite compound.
Another embodiment of the present invention provides a process for isomerizing 1,4-diacetoxy-2-butene to produce the corresponding allylic isomer, 3,4-diacetoxy-1-butene, wherein the isomerization is conducted in the presence of a catalyst containing a Group VIII-X metal compound and a phosphite compound.
Another embodiment of the invention provides a process for isomerizing a mixture of 3,4-diacetoxy-1-butene and 3-butene-1,2-diolmonoacetoxylate to produce a mixture of the corresponding allylic isomers, 1,4-diacetoxy-2-butene and 1-acetoxy-4-hydroxy-2-butene, wherein the isomerization is conducted in the presence of a catalyst containing a Group VIII-X metal compound and a phosphite compound.
Another embodiment of the invention provides a process for isomerizing a mixture of 3,4-disubstituted-1-butene and 3-butene-1,2-diolmonosubstituted to produce a mixture of the corresponding allylic isomers, 1,4-disubstituted-2-butene and 1-monosubstituted-4-hydroxy-2-butene, wherein the isomerization is conducted in the presence of a catalyst containing a Group VIII-X metal compound and a phosphite compound.
Another embodiment of the invention provides a process, that includes:
(1) diacetoxylating butadiene to obtain a mixture containing at least one selected from the group including 3,4-diacetoxy-1-butene, 3-butene-1,2-diolmonoacetoxylate and a mixture thereof, and at least one selected from the group including 4-diacetoxy-2-butene, acetoxy-4-hydroxy-2-butene and a mixture thereof;
(2) s
Hara Yoshinori
Ohno Hironobu
Retboll Mikael
Urata Hisao
Gitomer Ralph
Mitsubishi Chemical Corporation
Oblon & Spivak, McClelland, Maier & Neustadt P.C.
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