WO2001021667A1 - Divalent lanthanide reduction catalysts - Google Patents
Divalent lanthanide reduction catalysts Download PDFInfo
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- WO2001021667A1 WO2001021667A1 PCT/US2000/025520 US0025520W WO0121667A1 WO 2001021667 A1 WO2001021667 A1 WO 2001021667A1 US 0025520 W US0025520 W US 0025520W WO 0121667 A1 WO0121667 A1 WO 0121667A1
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/10—Polymerisation reactions involving at least dual use catalysts, e.g. for both oligomerisation and polymerisation
- B01J2231/12—Olefin polymerisation or copolymerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/38—Lanthanides other than lanthanum
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Definitions
- the present invention relates generally to the chemistry of inorganic reduction catalysts, and more particularly to the composition and use of dihalogenated Ianthanides catalysts to facilitate reduction reactions such as the preparation of alkylated hydrocarbons and/or organic polymers.
- the Ianthanides as a group are quite electropositive, for example electronegativities of samarium and ytterbium are 1.07 and 1.06, respectively, on the Allred-Rochow scale, and the chemistry of these elements is predominantly ionic. This may be because the 4 -electrons do not have significant radial extension beyond the filled 5s 2 5p 6 orbitals of the xenon inert gas core.
- the Ianthanides therefore behave as close-shell inert gasses with a tripositive charge, and in general electrostatic and steric interactions play a greater role in chemistry of the Ianthanides than do interactions between the metal and associated ligand orbitals.
- the ionic radii of the Ianthanides are large. Most transition metal ionic radii lie in the range from 0.6 to 1. ⁇ A, whereas the Ianthanides have an average ionic radius of approximately 1.2A. Divalent species are, of course, even larger, eight-coordinate Sm II has an ionic radius of 1.41 A, for example.
- the relatively large ionic radii of the Ianthanides allow the accommodation of up to 12 ligands in the coordination sphere, and coordination numbers of seven, eight and nine are common. Owing to the well known 'lanthanide contraction', ionic radii decrease steadily across the row of Ianthanides in the periodic table.
- the lanthanide contraction may be a consequence of poor shielding of the 4f-electrons, resulting in an increase effective nuclear charge and a concomitant decrease in ionic radius.
- higher coordination numbers are most common in the larger, early Ianthanides.
- HSAB hard and soft acids and bases
- lanthanide +3 ions are considered to be hard acids, falling between Mg (II) and Ti (IV) in the established scale.
- Lanthanides therefore complex preferentially to hard bases such as oxygen donor ligands.
- the present invention provides new divalent lanthanide reducing agents and methods for using such reducing agents.
- a method of reducing a compound to form a reduction product such method generally comprising the step of combining the compound with a divalent lanthanide reducing agent of General Formula A, as follows:
- M is a lanthanide other than the Europium, Ytterbium or Samarium;
- G 1 and G 2 may be the same or different chemical entity independently selected from a halogen, alkyl, aryl, NR 2 , OR 2 , PR 2 , or SR; wherein N is a nitrogen, O is an oxygen, P is a phosphorus and R is selected from the group consisting of an alkyl, an aryl, and a cycloalkyl from about 1 to about 20 carbon atoms.
- M may be Thulium, Dysprosium, Neodymium, Cerium, Praseodymium, Gadolinium, Terbium, Holmium, Erbium, Lutetium, Lanthanum or Yttrium.
- Gi and G 2 may be the same halogen, for example Iodine; or alternatively Gi and G 2 may be different halogens, such as Iodine and Chlorine (or Bromine). Still further in accordance with the invention, there is provided an embodiment wherein the divalent lanthanide reduction catalyst is thulium diiodide.
- the divalent lanthanide reduction catalyst is Dysprosium diiodide.
- a compound of formula A may be combined with a solvent (S), such that coordinate bond(s) are formed between the lanthanide M molecules and the solvent S molecules.
- the solvent S may be a Lewis base, for example: an ether (e.g. a di-alkyl-oxy- ethane), a furan (e.g. tetrahydrofuran), a diene (e.g. butadiene), a nitrile (e.g. acetonitrile) and other heteroatom donor bases.
- the complex formed by the combination of the lanthanide M and solvent S may have the General Formula B, as follows:
- M is a lanthanide other than the Europium, Ytterbium or Samarium;
- Gi and G 2 may be the same or different chemical entity independently selected from a halogen, alkyl, aryl, NR 2 , OR 2 , PR 2 , or SR; wherein N is a nitrogen, O is an oxygen, P is a phosphorus and R is selected from the group consisting of an alkyl, an aryl, and a cycloalkyl from about 1 to about 20 carbon atoms.; and,
- DME dimethoxyethane
- Figure 1 is a thermal ellipsoid plot of one of the independent Tml 2 (DME) 3 molecules in a unit cell, wherein ellipsoids are drawn at the 50% probability level.
- Figure 2 is a thermal ellipsoid plot showing the structure of Dyl 2 (DME) 3 with thermal ellipsoids drawn at the 50% probability level.
- the invention provides for a method of reducing a compound to form a reduction product.
- the compound according to this invention is preferably a reducible molecule, such as those containing at least one multiple bond, for example a carbon-carbon double bond, a carbon-carbon triple bond or a carbonyl in a cyclic or acyclic structure.
- the cyclic or acyclic structure optionally contains one or more heteroatoms.
- the compound according to this invention is an arene.
- the method comprises the step of combining the compound with a lanthanide catalyst, having General Formula A: wherein; M is a lanthanide other than the Europium, Ytterbium or Samarium;
- Gi and G 2 may be the same or different chemical entity independently selected from a halogen, alkyl, aryl, NR 2 , OR 2 , PR 2 , or SR; wherein N is a nitrogen, O is an oxygen, P is a phosphorus and R is selected from the group consisting of an alkyl, an aryl, and a cycloalkyl from about 1 to about 20 carbon atoms.
- Gi and G 2 are halogens, Gi being the first halogen and G 2 being the second halogen.
- Gi and G 2 are the same halogen, for example Iodine.
- Gi and G 2 are different halogens, for example Gi may be an Iodine and G 2 may be a Bromine or a Chlorine.
- a lanthanide catalyst may be employed to affect an alkylation of the compound to form an alkylated organic compound, which is a reduction product.
- the alkylated organic compound is a pharmaceutical compound, especially because unlike many of their main group and transition metal counterparts, inorganic lanthanide compounds are generally classified as nontoxic when introduced orally.
- samarium chloride and ytterbium chloride exhibit similar toxicity to that of sodium chloride (LD 50 of >2000-6700 mg/kg in mice versus 4000 mg/kg for NaCI).
- lanthanide complexes are converted to hydroxides immediately on ingestion, and thus have limited absorption through the digestive tract.
- Moderate toxicity may be exhibited by lanthanide salts introduced via the intraperitoneal route.
- the alkylation process may follow the general scheme:
- R may be an alkyl group and J may be a halogen, for example Iodine, fluorine, preferably Bromine or Chlorine; R' is the organic compound and RR' is the alkylated organic compound.
- the lanthanide catalyst in the alkylation process may include a Thulium diiodide.
- the lanthanide catalyst may include a Thulium diiodide (DME) 3 .
- Tm(ll) complex Tml 2 (DME) 3
- This complex is found to be structurally analogous to samarium diiodide in DME, but it is much more reactive since 4f 13 Tm(ll) has a much greater reduction potential than 4 Sm(ll).
- preliminary studies indicate that this compound is so reactive, that it is uncertain if this species would be useful as a reagent like Sml 2 (THF) x in organic transformations.
- Tml 2 (DME) ⁇ is viable as a reagent and if it has utility as an alternative for Sml 2 (THF) x /HMPA, we examine its reactivity in the coupling of 4-te/ ⁇ -butylcyclohexanone with alkyl halides, Scheme 1.
- Tml 2 (DME) 2 can be produced by reduction of a suspension of Tml 3 (DME) 2 (2.5 g, 3.4 mmol) in 50 mL of oxygen-free, dry DME with Tm powder (0.65 g, 3.86 mmol). The reaction is heated to reflux under nitrogen for 40 minutes and is filtered to remove unreacted Tm metal. Removal of the solvent under vacuum, leads to quantitative conversion to Tml 2 (DME) 2 (3.07 g, 5.1 mmol) as an emerald green powder.
- reaction is used as an assay, since it has been thoroughly studied with samarium diiodide. Reactions are carried out in accordance with the samarium Grignard procedure introduced by Curran et al., in which two equivalents of the lanthanide reagent are added to the alkyl halide and the ketone is added subsequently. Reactions using Sml 2 (THF) ⁇ /HMPA are conducted to insure that Sm/Tm comparisons could be made under one uniform set of conditions.
- HMPA-free Tml 2 (DME) ⁇ is at least equivalent to Sml 2 (THF) ⁇ /HMPA
- less reactive halides are examined. Reactions with alkyl bromides and Sml 2 (THF) ⁇ /HMPA are reported to occur, but at a much slower rate than iodides.
- Sml 2 (THF) ⁇ /HMPA required 15 minutes to change color from the deep purple of Sm(ll) to an orange-yellow characteristic of Sm(lll).
- Tml 2 (DME) x in DME (entry 6) reacts to give a yellow solution in 3 minutes, which after addition of the ketone results in a 79:21 ratio of a-4-tert- butyl-1 -phenethyl-cyclohexanol and ⁇ -4-te/ ⁇ -butyl-1 -phenethyl-cyclohexanol in 88% yield.
- Tml 2 (DME) ⁇ exhibits such high reactivity at room temperature, its viability at reduced temperature is examined.
- Tml 2 (DME) ⁇ is added as a DME solution by syringe using a saturated stock solution generated in situ from Tm and l 2 .
- Phenethyl iodide reacts smoothly at -22°C in 10 minutes to form phenethylcyclohexanoi in 96% yield (entry f).
- Tml 2 (THF) x generates conveniently in situ in THF as a stock solution on a Schenk line from Tm and l 2 , gave excellent results as well.
- Tml 2 has the potential to be an effective replacement for Sml 2 (THF) ⁇ when HMPA is to be avoided, when the Sml 2 (THF) ⁇ /HMPA system is too weak a reductant to accomplish a reaction, when sub-ambient reaction temperatures are desirable, and when reactions faster than those achievable via MX 2 and samarium addition and photolysis are needed.
- the higher reactivity of Tml 2 may limit its functional group tolerance in some applications, but it is possible that this can be overcome by developing the appropriate protocols.
- Thulium diiodide (DME) 3 As a catalyst to add alkyl groups to organic substrates
- the starting material for the alkylation process may be alkyl bromide and alkyl chloride reagents instead of the usual and more expensive alkyl iodides.
- it is safer, especially for the production of pharmaceutics.
- samarium diiodide has become a popular reducing agent in organic synthesis.
- reactivity may be enhanced by adding hexamethylphosphoramide (HMPA) to Sml 2 (THF) x .
- HMPA hexamethylphosphoramide
- THF hexamethylphosphoramide
- the following schemes 1 and 2 shows Tml 2 catalyzing the reaction of an alkyl halide with 4-fetf-butylcyclohexanone to give ⁇ tet_-butyl-1 -phenethyl- cyclohexanol, and ⁇ -tet ⁇ -butyl-1 -phenethyl-cyclohexanol; and Tml 2 (DME) 2 catalyzing an alkyl halide with 4-fetf-butylcyclohexanone to give ⁇ -4-tet.-butyl- 1-methyl-cyclohexanol, ⁇ -4-te/t-butyl-1-methyl-cyclohexanol, ⁇ -4-te/t-butyl-l- butyl-cyclohexanol and ⁇ -4-fe/f-butyl-1-butyl-cyclohexanol.
- R Bu ⁇ -4-tert-butyl-l-butyl-cyclohexanol ⁇ -4-tert-butyl- 1 -butyl-cyclohexanol
- Thulium diiodide (DME) 3 As the chemistry of Thulium diiodide (DME) 3 becomes more important it may be necessary to explore in detail the synthesis and structure of Thulium diiodide (DME) 3 . As discussed above, to date this important divalent 4f element chemistry has involved only three metals, Sm (II), Eu (II), and Yb (II). Divalent ions can be formed for all of the metals in the 4f series by high- temperature reduction of the halides with the metal or by radiolysis of trivalent metal ions trapped in crystalline lattices, but these insoluble and dilute systems are generally only characterized by spectroscopic means.
- the thulium atom in Tm 2 (DME) 3 is seven- coordinate; two DME ligands are chelating and one is monodentate. This is a rare example of a complex containing a monodenate DME ligand.
- the pentagonal-bipyramidal structure of Compound C is similar to those of the solvated divalent Samarium diiodide complexes, Sml 2 (THF)s (Compound D), Sml 2 (DME)(THF) 3 (Compound E) and Sml 2 (DME) 2 (THF) (Compound F).
- the halide ligands are in the axial positions and oxygen donor atoms are at the equatorial sites.
- the average l-Tm-l angle (174.3(5)°) in Compound C is similar to the l-Sm-l angles in Compound E and Compound F (178.8(1 )°).
- the l-Tm-O angles range from 79.7(4) to 102.8(3)° and thus deviate from the angle expected in a perfect pentagonal bipyramid (90°).
- the corresponding l-Sm-O angles in Compound E and Compound F range from 79.2(1°) to 100.6(1°).
- O-Tm-O angles for adjacent donor atoms (65.8(3)-80.5(5)°) is also similar to the corresponding range of O-Sm-O angles (63.6(l)-80.2(2)°) in Compound E and Compound F, and differs from the ideal angle of 72° because some of these angles involve a single chelating ligand and some are between ligands.
- the average Tm-I distance (3.16(2) A) in Compound C is in the range expected for a Tm(ll) complex.
- the Sm-I distances in Compound E and Compound F are 3.231 (l)-3.246(l) A, and the ionic radius of samarium is about 0.13 A larger than that of thulium.
- Tm-O distances (2.456(13)-2.546(14) A) for the two independent molecules in the unit cell is wider than the range observed for Sm(ll)-O(DME) distances (2.595(5)-2.646(4) A) in Compound E and Compound F, but again these distances are consistent with the presence of Tm(ll) after the difference in radius (0.13 A) is taken into consideration.
- Tm(ll)-O distances in Compound C are significantly different from the distances found in Tm(lll) complexes.
- Tm(lll)-O(THF) distances of 2.353(3) and 2.315(3) A have been reported in eight-coordinate [(C 8 H 8 )Tm ⁇ PhC(NsiMe 3 ) 2 )(THF)] and five-coordinate [Tm ⁇ P(SiMe3)2 ⁇ 3 (THF) 2 ], respectively.
- Tm(lll)-I distances are available for comparison, but Tm(lll) - Cl distances ranging from 2.585(4) to 2.667(2) A are found in the eight- coordinate complexes [TmCI 2 (OH 2 ) 2 ([12]crown-4)]CI and
- metal-chloride distances are typically 0.31-0.42 A shorter than metal-iodide distances
- analogous Tm(lll)-I distances would be in the range 2.89-3.09 A which is substantially shorter than those observed in Compound C.
- Tml 2 in THF prepared by heating Tml 3 with thulium metal in a welded tantalum crucible under argon at 800°C.
- the measured effective magnetic moment of Compound C (4.53 ⁇ B (293 K.)) matches the value of 4.5 ⁇ calculated for a 4F 13 electron configuration and found for isoelectronic Yb(lll) complexes. This value differs significantly from Tm(lll) magnetic moments which are typically 7.1-7.5 ⁇ e-
- Figure 1 further shows a thermal ellipsoid plot of one of the independent
- Selected bond lengths (A) are: Tml - 05 2.47 (2),
- UV/Vis (l.l ⁇ x 10 "3 M in DME, 20°C, ⁇ m a ⁇ ( ⁇ )): 298 (700), 416 (250), 562 (90), 624 (80) nm.
- the method of synthesizing the dihaiogenated lanthanide complex employs the step of refluxing under an inert gas, for example nitrogen, for about 30 to about 90 minutes, preferably 60 minutes. This step substantially eliminates the need for repeated vacuum transfers, providing for a simple and more efficient method of synthesizing lanthanide catalysts.
- Thulium diiodide (DME) X is clearly effective as a reducing agent, for example it may catalyze an addition reaction to a carbonyl moiety of a molecule better than the presently used catalysts, such as Sm (DME) X .
- the present invention includes other lanthanide catalysts as well.
- Dysprosium diiodide or Dysprosium diiodide (DME) X may also be employed as an effective lanthanide catalyst. Divalent ions of most of the lanthanides have been reported to form under extreme conditions in solid state lattices, isolation of easily accessible, soluble forms that would be used in organic synthesis seemed unlikely.
- Crystals of Dyl (DME) 3 prepared by the method of Bochkarev, are grown from DME at -20°C in a nitrogen-containing glove box over a period of 36 h. These crystals are found to be isomorphous with Sml2(DME) 3 . Since we are suspicious that we could actually isolate such a reactive species, the same crystal examine by X-ray diffraction is also examined by energy dispersive absorption X-ray spectroscopy (EDAX) which confirms that it is truly a dysprosium complex.
- EDAX energy dispersive absorption X-ray spectroscopy
- Dyl 2 (DME) 3 like its samarium analog, has an unusual structure in which there are two independent molecules in the unit cell, one of which has a linear l-Dy-l component and the other which has a bent l-Dy-l moiety, Figure 2.
- Figure 2 further shows structure of Dyl 2 (DME) 3 with thermal ellipsoids drawn at the 50% probability level.
- Each molecule has three chelating DME ligands that generate a hexagonal bipyramidal geometry in the linear l-Dy-l case and a distorted dodecahedral geometry in the bent l-Dy-l system. This differs from the structure of Tml 2 (DME) 3 which contains one DME and is seven coordinate. This difference is consistent with the smaller radial size of Tm.
- DME Tml 2
- Dyl 2 (DME) 3 Once the existence of Dyl 2 (DME) 3 is crystallographically established, we sought a more convenient preparation that would allow it to be used as a routine reagent.
- Solid Dyl 2 can be conveniently prepared in multi-gram quantities by reacting dysprosium filings and Iodine in an alumina or quartz crucible contained within a quartz tube connected to a Schlenk line.
- Dy filings (3.0 g, 18.4 mmol) are 25 spread evenly in a layer on the bottom of a 10-mL alumina or quartz crucible. Iodine (4.75 g, 18.7 mmol) is then layered on top of the metal.
- the charged crucible is placed in a 20x4.5 cm quartz test tube fitted with a 55/50 joint which is connected 30 to a trap and a Schlenk line in a well-shielded hood.
- the tube is evacuated and refilled with N2 three times to remove oxygen.
- the apparatus is under a nitrogen atmosphere connected to a mineral oil bubbler.
- the apparatus is tipped at a 60° angle to avoid directly heating the joint and the bottom of the tube containing the crucible is heated with a Meeker burner at maximum heat.
- the tube initially fills with l 2 vapor and a bright light flash indicates ignition of the metal. Heating of the initial mixture is continued at the bottom of the tube for about 2 min, during which time is consumed. Vacuum is then applied to transfer unreacted I 2 to the trap. A nitrogen atmosphere is reestablished in the vessel and heating is continued for 15 min during which time part of the mixture melts.
- the system is allowed to cool to room temperature and the apparatus is transferred to a nitrogen-filled glovebox.
- the solid mass of Dyl 2 is removed from the crucible with a spatula and crushed with a mortar and pestle.
- the unreacted metal (1.25 g), which is left as a nugget, is easily identified and removed while the Dyl 2 is being ground.
- Dyl 2 (3.8 g, 85% based on metal consumed) is recovered as a violet powder suitable for synthetic reactions. Since solutions in DME or THF are light and temperature sensitive, they should be prepared immediately before use.
- the solid mass of Dyl 2 that forms can be easily separated from residual metal.
- the Dyl 2 can be crushed with a mortar and pestle under an inert atmosphere and stored for long periods under nitrogen until needed.
- the steps of the present invention allows for the initial reaction to be followed by continual heating of about 1 to about 60 minutes, preferably about 30 minutes.
- the continual heating in accordance with the present invention produces a melt, which completes the reaction.
- 10 according to the present invention are a larger quantity of starting material (e.g. more than about 5 grams, preferably about 15 to about 20 grams) may be used and the percentage yield of the product is higher.
- Example 5 demonstrated one embodiment of how Dyl 2 may be synthesized, it is possible to synthesize other lanthanide catalysts, for example Tml 2 , using the methods as disclosed in Example 5 or modifications of such method as would be known to one of ordinary skill in the art. Since solutions of Dyl 2 are so reactive, they should be prepared immediately before use. Dyl 2 may be used conveniently by making a saturated solution in THF or DME at temperatures below -20°C. The solubility of Dyl 2 in THF is 0.025 M at -45°C. The utility of Dyl 2 (THF) x in ketone coupling reactions with alkyl halides appears to be similar to that of Tml 2 (THF) x except that Dy(ll) is much more reactive.
- Dyl 2 is a strong reducing agent, it is not a strong base.
- the addition of dry 2-propanol to a solution of Dyl 2 in DME at 25°C showed no color change even after 4hr.
- Dyl 2 is known to react quickly under the same conditions with difficult to reduce compounds such as naphthalene, so initially this observation is surprising. This is consistent with a compound that is a strong reducing agent, but not a strong base.
- Dyl 2 in DME is a strong enough reductant to immediately react with naphthalene at -45°C to form a dark purple solution from which
- Figure 3 shows the structure of (C-ioH 8 )Dyl(DME) 2 with thermal ellipsoids drawn at the 50% probability level.
- the selected bond lengths (A) are: Dy-01 , 2.467(3); Dy-O2, 2.562(4); Dy-O3, 2.411 (3); Dy-O4, 2.430(3); Dy-C1 , 2.510(5); Dy-C2, 2.599(5); Dy-C3, 2.605(5); Dy-C4, 2.486(5); Dy-C5, 2.992(5); Dy-CIO, 3.002(4); Dy-I, 3.1382(4).
- naphthalenide dianion complex The isolation of a naphthalenide dianion complex is not unique in f element chemistry and several examples are known. However, in each case, these have been formed by reduction of naphthalene with an alkali metal and reaction of the alkali metal naphthalene dianion with an / " element halide or by reaction of the lanthanide metal with naphthalene in liquid ammonia. This is the first case in which a low oxidation state lanthanide metal complex has reduced naphthalene directly in ethereal solvents.
- Dyl 2 (DME) 3 alone does not appear to reduce benzene or anisoles, but it will reduce alkynes. Reduction of PhC ⁇ CPh followed by hydrolysis forms exclusively cis-stilbene, Eq. 3.
- Dysprosium diiodide may also be used to catalyze the reduction of a double bond (or triple bond) containing molecule, for example, with other double bond (or triple bond) containing molecules to form a polymer.
- the polymerizable unit comprises ethylenically unsaturated monomers, such as: Monoolefinic hydrocarbons, i.e.
- monomers containing only carbon and hydrogen including such materials as butadiene, myrcene, ethylene, propylene, 3-methylbutene-1 , 4- methylpentene-1 , pentene-1 , 3,3-dimethylbutene-1 , 4,4-dimethylbutene-1 , octene-1 , decene-1 , styrene and its nuclear, alpha-alkyl or aryl substituted derivatives, e.g., o-, m- or p-methyl, ethyl, propyl or butyl styrene, alpha- methyl, ethyl, propyl or butyl styrene; phenyl styrene, and halogenated styrenes such as alpha-chlorostyrene; monoolefinically unsaturated esters including vinyl esters, e.g., vinyl acetate, vinyl propionate, vinyl butyrate, vinyl
- alkyl alpha-cyanoacrylates e.g., methyl alpha-chloroacrylate, ethyl alpha-chloroacrylate, methyl alphabromoacrylate, ethyl alpha-bromoacrylate, methyl alpha-fluoroacrylate, ethyl alpha-fluoroacrylate, methyl alpha-iodoacrylate and ethyl alpha- iodoacrylate
- alkyl alpha-cyanoacrylates e.g., methyl alpha-cyanoacrylate and eth
- Vinyl alkyl ethers and vinyl ethers e.g., vinyl methyl ether, vinyl ethyl ether, vinyl propyl ether, vinyl n-butyl ether, vinyl isobutyl ether, vinyl 2-ethylhexyl ether, vinyl-2- chloroethyl ether, vinyl propyl ether, vinyl n-butyl ether, vinyl isobutyl ether, vinyl-2-ethylhexyl ether, vinyl 2-chloroethyl ether, vinyl cetyl ether and the like; and vinyl sulfides, e.g., vinyl beta-chloroethyl sulfide, vinyl beta-ethoxyethyl sulfide and the like can also be included as can diolefinically unsaturated hydrocarbons containing two olefinic groups in conjugated relation and the halogen derivatives thereof, e.g
- the polymerizable unit comprises butadiene, myrcene or other dienes.
- the polymerizable unit comprises isoprene (2-methylbutadiene, the monomer in natural rubber).
- the reaction may be carried out in various solvents, for example neat, toluene, toluene with alkylaluminum, etc.
- a lanthanide catalyst according to this invention for example Dysprosium diiodide or Dysprosium diiodide (DME) 3
- DME Dysprosium diiodide
- the lanthanide catalyst used for the polymerization of isoprene is Dysprosium diiodide.
- the lanthanide catalyst according to this invention may also be employed in the synthesis of new types of elastomers. The gross physical properties of the polymers, which have been made, suggest that different types of polymers can be made by slightly changing the polymerization conditions.
- the method employing a lanthanide catalyst according to this invention to polymerize polymerizable units has a distinct advantage over the current methods.
- trivalent lanthanide compounds have been used to polymerize isoprene, but they involve at least two activators.
- the present method has a single component solid, for example Dysprosium diiodide or Dysprosium diiodide (DME) 3 , which could be added to monomer to cause polymerization.
- DME Dysprosium diiodide
- isoprene such as isoprene may be synthesized according to the following method. To a vial containing a solution of 5 mL of isoprene and 5 mL dissolved in hexanes, 10 mg of Dyl 2 is added. The suspension is allowed to stir for 8 hrs., after which a thick purple solution is
- a reduction product is made from a process which comprises the step of combining a compound with a lanthanide catalyst, preferably Dyl 2 , according to this invention.
- the compound comprises a polymerizable unit, for example dienes, preferably isoprene, and the reduced product is a polymer.
- the samples of polyisoprene obtained from reactions with Dyl 2 share the property of being soluble in non-polar solvents such as hexanes or heptane. This may allow for the production of blends of polyisoprene with other soluble polymer to produce a value-added product with unique properties.
- the catalytic lanthanide is Dysprosium diiodide (DME) 3 .
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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AU75885/00A AU7588500A (en) | 1999-09-21 | 2000-09-18 | Divalent lanthanide reduction catalysts |
US10/088,749 US6887824B1 (en) | 1999-09-21 | 2000-09-18 | Divalent lanthanide reduction catalysts |
EP00965109A EP1242468A1 (en) | 1999-09-21 | 2000-09-18 | Divalent lanthanide reduction catalysts |
Applications Claiming Priority (2)
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US15531099P | 1999-09-21 | 1999-09-21 | |
US60/155,310 | 1999-09-21 |
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WO2001021667A1 true WO2001021667A1 (en) | 2001-03-29 |
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PCT/US2000/025520 WO2001021667A1 (en) | 1999-09-21 | 2000-09-18 | Divalent lanthanide reduction catalysts |
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EP (1) | EP1242468A1 (en) |
AU (1) | AU7588500A (en) |
WO (1) | WO2001021667A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110809622A (en) * | 2017-06-19 | 2020-02-18 | 西姆莱斯有限公司 | Novel ambergris and/or indole aromatic composition |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6034190A (en) * | 1995-08-11 | 2000-03-07 | Sumitomo Chemical Company, Limited | Olefin polymerization catalyst component |
US6111082A (en) * | 1998-04-17 | 2000-08-29 | Rhodia Rare Earths Inc. | Stable concentrated rare earth carboxylate liquids |
-
2000
- 2000-09-18 EP EP00965109A patent/EP1242468A1/en not_active Withdrawn
- 2000-09-18 WO PCT/US2000/025520 patent/WO2001021667A1/en not_active Application Discontinuation
- 2000-09-18 AU AU75885/00A patent/AU7588500A/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6034190A (en) * | 1995-08-11 | 2000-03-07 | Sumitomo Chemical Company, Limited | Olefin polymerization catalyst component |
US6111082A (en) * | 1998-04-17 | 2000-08-29 | Rhodia Rare Earths Inc. | Stable concentrated rare earth carboxylate liquids |
Non-Patent Citations (2)
Title |
---|
EVANS ET AL.: "Ketone coupling with alkyl iodides, bromides and chlorides using thulium diiodide: A more powerful version of SmI2(THF)x/HMPA", J. AM. CHEM. SOC., vol. 122, no. 9, 2000, pages 2118 - 2119, XP002935238 * |
WINFIELD ET AL.: "Redox reactions between molybdenum or tungsten hexafluorides and p, f or d block elements in acetonitrile: Comparisons with reactions involving nitrosonium fluorometallates, the effect of fluoride ligand transfer and redox inhibition due to surface oxide", JOURNAL OF FLUORINE CHEMISTRY, vol. 91, 28 April 1998 (1998-04-28), pages 213 - 218, XP002935237 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110809622A (en) * | 2017-06-19 | 2020-02-18 | 西姆莱斯有限公司 | Novel ambergris and/or indole aromatic composition |
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EP1242468A1 (en) | 2002-09-25 |
AU7588500A (en) | 2001-04-24 |
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