Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Reexamination Certificate
1999-12-16
2002-02-26
Vollano, Jean F. (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
C568S841000, C568S842000
Reexamination Certificate
active
06350922
ABSTRACT:
BACKGROUND OF THE INVENTION
The present invention relates to a process for making 2,3-dihalopropanols utilizing an iridium metal plus a second transition metal mixed metal catalyst wherein the second transition metal comprises ruthenium, iron, molybdenum, tungsten, rhenium, osmium, manganese or vanadium.
Mixed transition metal catalysts have been made previously. For example, Hamada, et al., in Appl. Catal., 1986, 27, 265-73; and Sekiyu Gakkaishi 1998, 41, 66-70, incorporated herein by reference, report the preparation of iridium/ruthenium mixed metal heterogeneous catalysts for the hydrogenation of carbon monoxide and the hydrogenolysis of n-butane; Van Gruijthuijsen, et al., in J. Catal., 1997, 170, 331-345, incorporated herein by reference, report the preparation of iridium/iron mixed metal heterogeneous catalysts for the hydrogenation of carbon monoxide; and Kuwahara, et al., in Chemistry Letters, 1985, 205-206, incorporated herein by reference, report the preparation of iridium/molybdenum mixed metal heterogeneous catalysts for the hydrogenation of carbon monoxide.
U.S. Pat. No. 5,744,655 issued to Thomas et al., Apr. 28, 1998, discloses a process for making a 2,3-dihalopropanol by reacting 2,3-dihalopropanal with a hydrogenating agent in the presence of a transition metal-containing catalyst, under conditions such that 2,3-dihalopropanol is formed.
Several catalysts for the above reduction reaction of 2,3-dihalopropanol are disclosed in U.S. Pat. No. 5,744,655 and in U.S. patent application Ser. No. 994,208, entitled “Process For Making 2,3-Dihalopropanols” filed Dec. 19, 1997, by Thomas et al. including catalysts containing a “Group VIIIA metal selected from iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum and mixtures thereof.” The catalysts known in the prior art are selected to provide high conversion and selectivity in single batch-type reactions. No real emphasis is placed on catalysts with sustained conversion and selectivity.
It is desired therefore to provide a hydrogenation process for converting 2,3-dihalopropanal to 2,3-dihalopropanol using a transition metal catalyst wherein the catalyst provides sustained hydrogenation activity at high conversion and selectivity.
SUMMARY OF THE INVENTION
One aspect of the present invention is directed to the discovery of mixtures of an iridium metal, as a first transition metal, and a second transition metal selected from the group comprising ruthenium, iron, molybdenum, tungsten, rhenium, osmium, manganese or vanadium metal on a support useful as catalysts for the hydrogenation of 2,3-dihalopropanal to 2,3-dihalopropanol. The iridium metal plus the second transition metal used as a mixed metal catalyst efficiently converts 2,3-dihalopropanal with high selectivity to 2,3-dihalopropanol and also exhibits unexpected sustained activity for the hydrogenation reaction. No one prior to the inventors of the present invention has used an iridium/second transition metal mixture as a catalyst for the hydrogenation of 2,3-dihalopropanal to 2,3-dihalopropanol.
Another aspect of the present invention is a process to make 2,3-dihalopropanol using the above catalysts comprising the step of reacting 2,3-dihalopropanal with a hydrogenating agent in the presence of the above iridium/second transition metal mixed metal catalysts, under conditions such that 2,3-dihalopropanol is formed.
Yet another aspect of the present invention is a process to make epihalohydrin comprising the steps of:
(1)reducing 2,3-dihalopropanal to form 2,3-dihalopropanol as described above; and
(2)cyclizing 2,3-dihalopropanol to make epihalohydrin.
This process for producing epihalohydrin advantageously uses only about one mole of molecular halogen per mole of epihalohydrin produced. This process reduces the amount of halogenated organics in the waste stream by more than 60 percent, relative to the commercial allyl chloride route. This process also uses substantially less water than the allyl chloride route. The reducing agent may be hydrogen, so that there is no need to recycle ketone to alcohol, as in transfer hydrogenation.
DETAILED DESCRIPTION OF THE INVENTION
The process of the present invention for making 2,3-dihalopropanol from a 2,3-dihalopropanal, generally, is a reduction reaction of an aldehyde to an alcohol. The reduction is carried out by hydrogenating a dihalopropanal to a dihalopropanol in the presence of a catalyst.
The catalysts useful in the present invention are selected such that under reaction conditions they catalyze the hydrogenation of substantially all of the aldehyde moieties on the dihalopropanal molecule to primary alcohol moieties without substantially affecting the halogens which are bonded to the molecule. The catalyst is advantageously a combination of iridium metal with a second transition metal comprising ruthenium, iron, molybdenum, tungsten, rhenium, osmium, manganese or vanadium in an effective ratio to provide a sustained high catalytic activity and a high selectivity to the dihalopropanol.
As an illustration of the present invention, for example, for iridium/ruthenium mixed metal catalysts the atomic ratio of iridium metal to ruthenium metal in the catalyst is generally from about 0.02 to about 15, preferably from about 0.05 to about 10, more preferably from about 0.15 to about 8, and most preferably from about 0.3 to about 2.0.
The selectivity for 2,3-dihalopropanol formation using the iridium/ruthenium mixed metal catalysts is greater than about 75%, preferably greater than 80% and more preferably greater than 90%.
The catalyst useful in the present invention also preferably has an initial catalyst activity in batch reactions of greater than about 50% dihalopropanal conversion at 30 minutes for a first charge of 2.5 grams dihalopropanal/gram catalyst and a second measured catalyst activity using the same catalyst of at least greater than about 50% dihalopropanal conversion at 30 minutes for a second charge of 2.5 grams dihalopropanal/gram catalyst. Although these are the preferred initial catalyst activities for a first charge of 2.5 grams dihalopropanal/gram catalyst, the catalyst can certainly be reacted with charges of less than 2.5 grams dihalopropanal/gram catalyst.
The catalyst useful in the present invention may be in homogeneous or heterogeneous form. Preferably, the catalyst is a heterogeneous catalyst.
The heterogeneous catalysts useful in the present invention may be, for example, an iridium metal and a second transition metal deposited or absorbed on an insoluble support such as silica, silylated silica, carbon, alumina, zirconia, titania, magnesia, and other common supports known in the art. Supports which can be used in the present invention are described in Poncelet et al. editors,
Preparation of Catalysts III
, New York, 1983; P. N. Rylander,
Hydrogenation Methods
, Academic Press, London, 1985; P. N. Rylander,
Catalytic Hydrogenation Over Platinum Metals
, Academic Press, New York, 1967; P. Rylander,
Catalytic Hydrogenation in Organic Syntheses
, Academic Press, New York, 1979, incorporated herein by reference. Also, the heterogeneous catalyst useful in the present invention may be an iridium metal and a second transition metal coordinated to ligands bonded to a resin, for example, on phosphinated polystyrene. The total weight percent of metal loading on the support is preferably from 0.001 to about 50 weight percent, more preferably from 0.01 to about 10 weight percent; and most preferably 0.05 to about 5 weight percent.
The homogeneous catalyst useful in the reaction mixture of the present invention contains mixtures of soluble iridium and second transition metal compounds or a soluble iridium/second transition metal mixed metal complex. Examples of soluble metal compounds include halides, acetoacetates, acetates and hydroxides of iridium and the second transition metal. A homogeneous catalyst useful in the present invention includes, for example, a RuCl
3
and IrCl
3
mixture.
The homogeneous catalysts useful in the present invention may further contain a coordinating ligand
Campbell Robert M.
Hucul Dennis A.
Ito Larry N.
Maughon Bob R.
Vosejpka Paul C.
The Dow Chemical Company
Vollano Jean F.
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