Sumitomo process

MIBK Direct Conversion ofMcetone over Heterogeneous Catalyst-Sumitomo, Process Evaluation Research Planning (PERP), Topical Reports, Vol. Ill, Chem Systems Inc., Tarrytown, NY, 1988. 

The catalytic asymmetric cyclopropanation of an alkene, a reaction which was studied as early as 1966 by Nozaki and Noyori,63 is used in a commercial synthesis of ethyl (+)-(lS)-2,2-dimethylcyclo-propanecarboxylate (18) by the Sumitomo Chemical Company (see Scheme 5).64 In Aratani s Sumitomo Process, ethyl diazoacetate is decomposed in the presence of isobutene (16) and a catalytic amount of the dimeric chiral copper complex 17. Compound 18, produced in 92 % ee, is a key intermediate in Merck s commercial synthesis of cilastatin (19). The latter compound is a reversible... 

Scheme 37 Synthesis of indomethacin Sumitomo process (Yamamoto et al., 1968).

There are now two plants operating in Europe, both located in Switzerland. The plant developed by Batrec AG in Wimmis has been in operation since 1994 and has a nominal capacity of 2000 tonnes of UDBs per annum. This plant is based on the Sumitomo process its flow sheet is shown schematically in Fig. A3.1. 

Flow diagram of the Sumitomo process for making a mixture of alumina and silica fibre (reproduced by permission of Chapman Hall)56. 

Figure 24 Synthesis of E-caprolactam by the EniChem-Sumitomo process.

Regioselective dimerization of propene to 2,3-dimethylbutenes (DMBs) is currently operated by Sumitomo and BP Chemicals. Both use P(cyclohexyl)3 as the bulky ligand. In the Sumitomo process [7] very high selectivities in DMBs (up to 85 %) are obtained at 20-50 °C, thanks to a sophisticated, highly efficient, Ziegler-type catalyst system (ten times more efficient than those of conventional catalysts) and by using toluene as a solvent. Isomerization of 2,3-dimethyl-1-butene (DMB-1) into 2,3-dimethyl-2-butene (DMB-2) takes place directly in... 

A membrane designated "Solrox" made by Sumitomo Chemical Company is closely related to the above plasma polymerized composite membranes. A 1980 report by T. Sano described the Sumitomo process (31). A support film was cast from a polyacrylonitrile copolymer containing at least 40 mole percent acrylonitrile. The support film was dried and exposed to a helium or hydrogen plasma to form a tight cross-linked surface skin on the porous polyacrylonitrile support film. Data in a U.S. Patent issued in 1979 to Sano et al showed that the unmodified support film had a water flux of 87 gfd (145 L/ sq m/hr) at 142 psi (10 kg/sq cm). After the plasma treatment a reverse osmosis test using 0.55 percent NaCl at 710 psi (4895 kPa) showed 10.5 gfd (17.5 L/sq m/hr) flux at 98.3 percent salt rejection (32). This membrane appears to fall between a conventional asymmetric membrane and a composite membrane. If the surface skin is only cross-linked, one might call it a modified asymmetric membrane. However, if the surface skin is substantially modified chemically to make it distinct from the bulk of the membrane it could be considered as a composite type. 

Not only strong acid sites but also relatively weak acid sites could be utilized in the development of improved industrial processes. One of the most significative examples is the new Sumitomo process for caprolactam manufacture, which combines a first step of ammoximation (originally developed by the Eni group [241-243]) with a second step of Beckmann rearrangement based on the use of silicalite-1 (Eigure 2.32). 

The conventional process (Figure 2.32a) involves the reaction of cyclohexanone tvith hydroxylamine sulfate (or another salt), producing cyclohexanone oxime that is subjected to the Beckmann rearrangement in the presence of stoichiometric amounts of sulfuric acid or oleum. The overall process generates about 4.5 kg of ammonium sulfate per kg of caprolactam, divided roughly equally over the two steps. The Sumitomo process (Figure 2.32b) instead produces virtually no waste and allows caprolactam to be obtained in >98% yield (based on cyclohexanone 93% based on FI2O2). 

Note that in all textbooks of green chemistry the new Sumitomo process of caprolactam synthesis is given as an example, because it eliminates ammonium sulfate generation, while, usually, the DSM route is not considered. In reality, ammonium sulfate generation is only one aspect of the impact on the environment. 

The First Industrial PO-Only Synthesis the Sumitomo Process... 

Figure 6.3 shows a simplified potential flow-sheet of the Sumitomo process, as inferred from the vast patent literature dating from 1999 onwards [6]. Here, two different layouts are hypothesized for the section aimed at the purification of PO in both cases, however, the key separation is an extractive distillation. It is reported that in these columns the highest temperature must not exceed 130 °C, to avoid the formation of heavy compounds. 

Figure 6.3 Simplified flow sheet of the Sumitomo process for PO synthesis, as inferred from the patent literature [5, 6]. 

Figure 12. Sumitomo-process for the production of S-cthylidcnebicyclo[2.2.1) hcpt-2-cnc.

Figure 1.15 Process flow diagram for the oxidation of propylene with cumene hydroperoxide as the oxidizing agent and titanium-containing mesoporous material as the heterogeneous catalyst (Sumitomo process). The process involves the following steps (1) A process for oxidation of cumene with air to obtain CMHP, (2) a process for epox-idation of propylene in the presence of a catalyst whereby o,a-dimethyl benzyl-alcohol CMA) is concomitantly obtained from CMHP, (3) a process for the hydrogenation of CMA with H2 i n the presence of a catalyst to obtain cumene, (4) a process for purification of the cumene, followed by recycle of cumene to the oxidation process, and (5) a process for the purification of PO. Adapted from Ref. (271), with permission from Wiley-VCH.

Applications to Diazepam Synthesis. The Sumitomo process for diazepam is depicted below (11). According to some reports, this is a major route by which diazepam (Valium), a widely-prescribed anti-anxiety drug, is prepared on an industrial scale. I have highlighted three reactions in the Sumitomo synthesis. These reactions involve toxic or corrosive reagents which would best be avoided if pollution control is an objective. It is worth noting that almost all of the other publish pathways for the synthesis of diazepam involve Friedel Crafts reactions in the key carbon-carbon bond forming step. 

T. Sano, T. Shimomura, M. Sasaki, I. Murase, Ichiki (Sumitomo) Process for producing semipermeable membranes,. US Patent 4107049, 1978. 

Toxco process and Sony/Sumitomo process are the oldest industrial methods of lithium battery recycling. The Canadian company uses mechanical and hydrometallurgical... 

FIGURE 9.23. Sumitomo process combined ammoximation and vapor phase Beckmann rearrangement for caprolactam synthesis. 

Sumitomo of Japan has developed a commercially alternative process that avoids the use of sulfuric acid and the concomitant undesired salt formation (see reaction sequence below). This alternative route is analogous to the cumene process for phenol production. Diisopropylbenzene (m-DIPB) can be manufactured by the catalytic dialkylation of benzene with two equivalents of propylene. The resulting m-DIPB is then catalytically hydroperoxidized to the corresponding dihydroperoxide (DHP). Upon acidification the dihydroperoxide (DHP) is cleaved cleanly to give resorcinol and acetone. It is worth noting that the Sumitomo process not only provides a cleaner alternative route for the production of resorcinol,... 

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