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Zoeller and Barnette 393tributyl amine can be dried by azeotropic distillation and reused in producing thenext batch of methyl pivaloylacetate. (Bu 3 N forms a minimum boiling azeotropewith water.) The resultant effluent from the reactor is a stream representing 1.5 molof innocuous NaCl resulting from the neutralization.In summary, compared with earlier processes which utilize hazardous solventsand generate large waste streams, the carbonylation of chloropinacolone offers anenvironmentally and operationally advantaged process since it requires (i) very littleexcess amine or methanol, (ii) no extraneous reaction solvents, (iii) little or noextraction solvent, and (iv) the tributylamine coreactant and methanol componentsare readily recycled. This was accomplished while also demonstrating similar yields,shorter reaction times, and higher product concentrations which result in a significantreduction in the number of batches and time required to produce significantquantities of methyl pivaloylacetate.Experimental SectionScreening Reactions.The following general procedure is typical for the screening reactions.To a 300 mL Hastelloy-B autoclave was added 110 mL (87.0 g, 2.71 mol) ofmethanol, 30.0 mL (23.3 g, 126 mmol) of tributyl amine, 11.0 mL (11.3 g, 83.8mmol) of 1-chloropinacolone, and 0.1 mmol of catalyst. The autoclave was sealed,flushed with carbon monoxide, and pressurized to 30 psi with CO. The autoclavewas then heated to 105°C and the pressure was adjusted to 80 psi. The temperatureand pressure were maintained using a continuous carbon monoxide feed for 3 h. Themixture was then cooled and analyzed by gas chromatography. Phosphine effectsand additional comparison were conducted at 150 psi of CO as noted in the tables.Catalyst Optimization.The following procedure is typical for optimizing the catalyst utilizing low catalystand methanol concentrations.To a 300 mL Hastelloy-B autoclave was added 31.0 mL (24.5 g, 765 mmol)of methanol, 90.0 mL (70.0g, 378 mmol) of tributyl amine, 33.0 mL (33.8 g, 251mmol) of 1-chloropinacolone, 14.0 mg (0.019 mmol) of [(cyclohexyl) 3 P)] 2 PdCl 2 , and28.0 mg (0.1 mmol) of tricyclohexylphosphine. The autoclave was sealed, flushedwith carbon monoxide, and pressurized to 30 psi with CO. The autoclave was thenheated to 120°C and the pressure was adjusted to 150 psi. The temperature andpressure were maintained using a continuous carbon monoxide feed for 3 h. Themixture was then cooled to yield a two phase reaction product. The entire productmixture (both layers) was diluted with 50.0 mL (39.55 g) of methanol to generate ahomogeneous mixture and analyzed by gas chromatography. Variations in theprocedure regarding temperature, pressure, catalyst levels (phosphine and Pd) areindicated in the tables and text.
394 Carbonylation of ChloropinacoloneAcknowledgementsThanks to Eastman Chemical Company for permission to publish this work and Dr.Robert Maleski for helpful discussions in initiating this effort.References1. K. Harada, S. Yamada and M. Ogami, Jap. Pat. 09110793 (A2) to UbeIndustries, Ltd (1997).2. K. Harada, S. Yamada and M. Oogami, Jap. Pat. 07215915 to Ube Industries,Ltd. (1995).3. G. Renner, I. Boie, and Q. Scheben, GB 1,491,606 to AGFA-Gavaert, A.G.(1977).4. M. Eyer, U.S. Pat. 5,144,057 to Lonza, Ltd.(1992).5. S. Yamada, Y. Oekda, T. Hagiwara, A. Tachikawa, K. Ishiguro, and S. HaradaU.S. Pat. 6,570,035 B2 to Takasago International Corp. (2003).6. R. A. Sheldon and H. J. Heijmen, U.S. Pat. No. 4,656,309 to Shell Oil Co.(1987).7. Y. Sun and C. Yao, Huanong Shikan, 15, 33 (2001).8. N. W. Boaz and M. T. Coleman, U.S. Pat. No. 6,143,935 to Eastman ChemicalCompany (2001).9. K. Harada and S. Ikezawa, Jap. Pat. 06279363 to Ube Industries, Ltd JP (1994).10. K. Harada, S. Ikezawa and M. Oogami, Jap. Pat. 06279362 to Ube Industries,Ltd. (1994).11. H. Iwasaki, H. Koichi, and T. Hosogai, Jap. Pat. 3371009 to Kuraray Co., Ltd.(2003).12. G. Renner, I. Boie and Q. Scheben, US Pat. No. 4,031,130 to AGFA-Gavaert,A.G. (1977).13. M. W. Rathke and P. J. Cowan, J. Org. Chem., 50, 2622 (1985).14. M. Vlassa and A. Barabas, J. fur Praktische Chemie (Liepzig), 322, 821 (1980).15. E. Sato and T. Furukawa, Jap. Pat. 10025269 A2 to Osaka Yuki Kagaku KogyoCo., Ltd. (1998).16. Y. Suenobe, N. Hanayama, T. Miura, and M. Kasagi, Jap. Pat. 63057416 toYoshitomi Pharmaceutical Industries, Ltd. (1988).17. P. N. Mercer, unpublished results.18. J. K. Stille and P. K. Wong, J. Org. Chem., 40, 532 (1975).19. A. L. Lapidus, O.L. Eliseev, T. N. Bondarenko, O.E. Sizan, and A. G.Ostapenko, Russian Chemical Bulletin, Int. Edit., 50, 2239 (2001)20. A. L. Lapidus, O.L. Eliseev, T. N. Bondarenko, O.E. Sizan, A. G. Ostapenko,and I. P. Beletskya, Synthesis, 317 (2002).21. V. Calo, P. Giannoccaro, A. Nacci, and A. Momopoli, J. Organomet. Chem.,645, 152 (2002).
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To Zsuzsanna and Tim
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Jones et al. 31. On the Use of Immo
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Jones et al. 5three-phase tests in
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Jones et al. 7In the HKR of rac-epi
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Moses et al. 132. Supported Re Cata
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Moses et al. 15perrhenate, followed
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Moses et al. 17SnCOSnMe 4≡SiOReO
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Moses et al. 19(AlOSi) of the cube.
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Moses et al. 212.510 3 k obs / s -1
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Wang et al. 233. Catalytic Hydrogen
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Wang et al. 25The rate expressions
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Wang et al. 27Schiff’s base forma
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32Halophosphite LigandsIn 1970, Pru
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34Halophosphite LigandsThe ligands,
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36Halophosphite LigandsTable 2 Temp
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38Halophosphite Ligands3. P. W. N.
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40Monolithic Bioreactorstrength for
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42Monolithic BioreactorMenten equat
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Gőbölös et al. 47was practically
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Gőbölös et al. 51Figure 2 NMR sp
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56Hydrotalcite-like Catalysts[A n-
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58Hydrotalcite-like Catalystssample
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68Synthesis of MIBKwe examined the
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70Synthesis of MIBK1412Conversion (
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72Synthesis of MIBK4,4’-dimethyl
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74Synthesis of MIBKobtained for MIB
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Ardizzi et al. 7710. The Control of
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Ardizzi et al. 79type acidity at th
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84Phenol Benzoylationconsecutive Fr
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86Phenol BenzoylationThis does not
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92Oxidation with Microchannel Immob
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100 Propylene Partial OxidationThe
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102 Propylene Partial OxidationSiO
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106 Propylene Partial Oxidation0.02
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108 Propylene Partial OxidationRefe
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110Oxidation of n-Pentanemethacryli
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112Oxidation of n-PentaneFReqox1ox2
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114Oxidation of n-Pentanethe presen
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116Oxidation of n-PentaneIn the mec
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118Oxidation of n-PentaneReferences
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120TEMPO Oxidation of Alcoholsthe u
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122TEMPO Oxidation of AlcoholsThe r
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124TEMPO Oxidation of Alcoholsany d
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126TEMPO Oxidation of Alcoholsconce
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128TEMPO Oxidation of AlcoholsMNT :
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130TEMPO Oxidation of Alcoholsuptak
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132Aminoalcohols to Aminocarboxylic
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142Bromine-Free TEMPO-Based Catalys
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148CO OxidationP25 TiO 2 , respecti
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150CO Oxidation0.02(a)21802110(b)21
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152CO Oxidationcarboxylate species
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Yamauchi 15519. 2006 Murray Raney A
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Yamauchi 157transformation is schem
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Yamauchi 159The X-ray diffraction p
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Yamauchi 163shown in Fig. 12. It wa
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168Nitrobenzene Hydrogenationfurthe
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170Nitrobenzene Hydrogenationhydrog
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172Nitrobenzene HydrogenationThe co
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174Nitrobenzene HydrogenationHence
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176Nitrobenzene Hydrogenation10. G.
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178 Hydrogenation of Dehydrolinaloo
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200 Fructose HydrogenationTable 1.
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Kuusisto, Mikkola and Salmi 237100A
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242 1-Phenyl-1-Propyneof cis-β-met
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294Chiral Ferrocene Ligandsnew Twin
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296Chiral Ferrocene LigandsTable 1.
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298Chiral Ferrocene Ligandsprevents
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300Chiral Ferrocene LigandsConclusi
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302Chiral Ferrocene Ligandsextracte
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304 Catalyst Library DesignIn gas p
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306 Catalyst Library Designd−(b 0
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312 Catalyst Library DesignCatalyst
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314 Catalyst Library Design27. S. H
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316 Dendrimer TemplatesWe are devel
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318 Dendrimer TemplatesThe differen
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320 Dendrimer TemplatesWe encounter
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322 Dendrimer TemplatesThe 100 cm -
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328Rearrangement of 3,4-Epoxy-1-But
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448Propylene Oxidation to POSupercr
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450Propylene Oxidation to POTable 1
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452Propylene Oxidation to PO
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464 Chiral 2-Amino-1-Phenylethanolp
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466 Chiral 2-Amino-1-PhenylethanolI
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468 Chiral 2-Amino-1-Phenylethanola
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470 t-Butanol DehydrationResults an
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472 t-Butanol Dehydrationcomprises
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482 Reductive AlkylationSince the p
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484 Reductive AlkylationTable 2. Re
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502 Electroreductive Catalytic Ullm
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504 Electroreductive Catalytic Ullm
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Catalysis of Organic Reactions 509K
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Catalysis of Organic Reactions 511T
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514 Keyword Indexcarboncarbon dioxi
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516 Keyword Indexethanolamine 16 13
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518 Keyword IndexNi, activated 25 2
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520 Keyword Indexsuccinimido ketone
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