Liquid products yields with various catalysts

The addition of hydrogen fluoride to acetylene has been widely investigated because the initial product, vinyl fluoride, is a commercially important monomer Acetylene reacts with hydrogen fluoride in the liquid phase in the absence of catalyst to give vinyl fluoride and 1,1 -ditluoroethane in modest yields [7 ], but better results are achieved by conducting the addition with various additives or catalysts... 

Composite samples of the total liquid product from each test were fractionated to determine the degree of hydrocracking attained with each catalyst. Distribution of the various distillate fractions for the tests made at 1500 psig are shown in Figure 4. Yields of naphtha and light oil were uniformly lower for tests made at 1000 psig. The highest vol % yields of liquid product were attained with catalysts I (Co-Mo) and... 

Hydrogenation. Gas-phase catalytic hydrogenation of succinic anhydride yields y-butyrolactone [96-48-0] (GBL), tetrahydrofuran [109-99-9] (THF), 1,4-butanediol (BDO), or a mixture of these products, depending on the experimental conditions. Catalysts mentioned in the literature include copper chromites with various additives (72), copper—zinc oxides with promoters (73—75), and mthenium (76). The same products are obtained by liquid-phase hydrogenation catalysts used include Pd with various modifiers on various carriers (77—80), Ru on C (81) or Ru complexes (82,83), Rh on C (79), Cu—Co—Mn oxides (84), Co—Ni—Re oxides (85), Cu—Ti oxides (86), Ca—Mo—Ni on diatomaceous earth (87), and Mo—Ba—Re oxides (88). Chemical reduction of succinic anhydride to GBL or THF can be performed with 2-propanol in the presence of Zr02 catalyst (89,90). 

There have been many efforts to commercialize 2,6-dicarboxynaphthalene for the preparation of poly(ethylene-2,6-naphthalate) due to its favorable thermoplastic properties compared with PET. Therefore, there are numerous patents in which 2,6-alkyl-substituted (alkyl = methyl, ethyl, isopropyl) naphthalenes are oxidized to the corresponding aromatic di-acids, applying mostly Co/Mn/Br catalysts with various co-catalysts such as Zr or Pd in acetic acid as the solvent. The major byproduct is formed by the oxidation of the naphthalene ring to give trimellitic acid (TMA) [5a, 8]. Sumikin Chemical has developed a method to prepare 2,6-naphtha-lenedicarboxylic acid by oxidation of 2,6-diisopropylnaphthalene (2,6-DIPN) in the liquid phase with air in a 500 tpy plant. Sumikin uses a newly developed catalyst based on Co/Mn with an addition of a few ppm of Pd giving advantages such as yields higher than 90 %, suppression of TMA production to around 1 %, and thus better catalyst recovery, and reduced consumption of acetic acid. 

This may be attributed due to the ability of [MOEMIM][TFA] to hydrogen bond with aromatic/heterocyclic/l,2-phenylenediamine. Smdies for recyclability of the regenerated ionic liquids cleared that the yield of the products decreases in various cycles, yet ionic liquid can be reused with significant success. The absence of catalyst and recyclability of ionic liquid make this procedure cleaner and promising for scale-up. 

In our discussion up to this point, comparisons of catalysts have been made with regard to activities and yields of various products. The products have included H2, C,-C4 hydrocarbons, and the C5-f liquid reformate. The yields of specific aromatic hydrocarbons in the reformate are also of interest. Data on yields of benzene, toluene, and total aromatic hydrocarbons in the reformate are summarized in Table 5.4 for platinum-iridium and platinum-rhenium catalysts in the reforming of the various naphtha fractions (33). For one of the naphthas, data are also shown for the combined catalyst system. The data shown are average values for the runs. 

In these cases, NFSI was preferred to Selectfluor and the reactions were performed either in alcohol or in ionic liquids in which the palladium complexes can be immobilized and reused with excellent reproducibility even after 10 consecutive cycles. For example, the enantioselective electrophilic fluorination of 2-methyl-3-oxo-3-phenylpro-pionic acid tert-butyl ester in [hmim] [BF4] gives the corresponding fluorinated product in 93% yield with 92% ee, and still in 67% yield with 91% ee after 10 cycles. The fluorination of various cyclic and acyclic (3-keto esters was carried out with NFSI in ethanol in the presence of 2.5 mol% of catalyst, leading to excellent ee-values up to 94%. The reaction is not sensitive to water, can be run on a 1-g scale, and proceeds via a palladium enolate complex as for the titanium-4,5-bis(diphenylhydroxymethyl)-2,2-dimethyl-dioxolane (TADDOL) catalyst. The reaction was extended to tert-butoxycarbonyl lactones and lactams. Reactions with lactones proceeded smoothly in an alcoholic solvent with 2.5 mol% of catalyst and NFSI, while the less acidic lactam substrates required concurrent use of the Pd complex and 2,6-lutidine as a co-catalyst. Under the reaction conditions, the fluorinated lactones and lactams were obtained in good yields with excellent enantioselectivities (up to 99%... 

---