Sebacic acid process

Sumimoto introduced a new sebacic acid process including several catalytic hydrogenation reactions.342 The synthesis starts with naphthalene, which is first partially hydrogenated to tetralin over cobalt oxide or molybdenum oxide, then to decalin over ruthenium or iridium on carbon. The selectivity to cw-decalin is better than 90%. In a later phase of the synthesis 5-cyclododecen-l-one is hydrogenated over Raney nickel to obtain a mixture of cyclododecanone and cyclodode-canol in a combined yield of 90%. The selectivity of this step is not crucial since subsequent oxidation of either compound leads to the endproduct sebacic acid. 

On the anodic side, four cases of undivided cells and two cases of divided cells have been chosen. Two processes are direct and four are indirect anodic oxidations. The sebacic acid process, as described by Asahi Chemical [74], is the industrial realization of the oldest and most thoroughly studied electrochemical reaction, the Kolbe reaction. 

The by-product of this process, pelargonic acid [112-05-0] is also an item of commerce. The usual source of sebacic acid [111-20-6] for nylon-6,10 [9008-66-6] is also from a natural product, ticinoleic acid [141-22-0] (12-hydroxyoleic acid), isolated from castor oil [8001-79-4]. The acid reacts with excess sodium or potassium hydroxide at high temperatures (250—275°C) to produce sebacic acid and 2-octanol [123-96-6] (166) by cleavage at the 9,10-unsaturated position. The manufacture of dodecanedioic acid [693-23-2] for nylon-6,12 begins with the catalytic trimerization of butadiene to make cyclododecatriene [4904-61-4] followed by reduction to cyclododecane [294-62-2] (see Butadiene). The cyclododecane is oxidatively cleaved to dodecanedioic acid in a process similar to that used in adipic acid production. 

Sebacic Acid. This acid is produced commercially by Union Camp in Dover, Ohio, by Hokoku OU Company in Japan, and by a state enterprise in the People s RepubHc of China (57). The process used in each case is based on the caustic oxidation of castor oU or ricinoleic acid [141-22-0] in... 

A number of process improvements have been described, and iaclude the use of white mineral oil having a boiling range of 300—400°C (60) or the use of a mixture of cresols (61). These materials act to reduce the reaction mixture s viscosity, thus improving mixing. Higher sebacic acid yields are claimed by the use of catalysts such as barium salts (62), cadmium salts (63), lead oxide, and salts (64). 

An electrooxidation process was developed by Asahi Chemical Industry ia Japan, and was also piloted by BASF ia Germany. It produces high purity sebacic acid from readily available adipic acid. The process consists of 3 steps. Adipic acid is partially esterified to the monomethyl adipate. Electrolysis of the potassium salt of monomethyl adipate ia a mixture of methanol and water gives dimethyl sebacate. The last step is the hydrolysis of dimethyl sebacate to sebacic acid. Overall yields are reported to be about 85% (65). 

Another alternative method to produce sebacic acid iavolves a four-step process. First, butadiene [106-99-0] is oxycarbonylated to methyl pentadienoate which is then dimerized, usiag a palladium catalyst, to give a triply unsaturated dimethyl sebacate iatermediate. This unsaturated iatermediate is hydrogenated to dimethyl sebacate which can be hydrolyzed to sebacic acid. Small amounts of branched chain isomers are removed through solvent crystallizations giving sebacic acid purities of greater than 98% (66). 

Saponins la 7,411,430 -, bioautographic determination la 109 Sarcosine Ia435 lbl24 Scandium cations, detection la 144 Scanner, optical trains la 30,39 S-Chamber (small chamber) la 126,127 SCHiFF s bases lb 52 Scintillators la 12 Scopolamine lb 231,252,255,323 Scopoletin lb 216-218,365 Screening process lb 45 Sebacic acid la 178,233,249,308 Sebuthylazine lb 418 Selectivity, enhancement by derivatiza-tion la 55... 

Cortisone acetate has been incorporated into several polyanhydrides (15). The rates of release of cortisone acetate from microcapsules of poly(terephthaUc acid), poly(terephthaUc acid-sebacic acid) 50 50, and poly(carboxyphenoxypropane-sebacic acid) 50 50 are shown in Fig. 8. These microcapsules were produced by an interfacial condensation of a diacyl chloride in methylene chloride with the appropriate dicarboxylic acid in water, with or without the crosslinking agent trimesoyl chloride. This process produces irregular microcapsules with a rough surface. The release rates of cortisone acetate from these microcapsules varied correspondingly with the rate of degradation of the respective polyanhydrides. It can be expected that the duration of release of cortisone acetate from solid microspheres, such as those produced by the hot-melt process, would be considerably longer. 

In Russia in the 1960s, an industrial production of sebacic acid, HCOOC (CH2)4 COOH (an important intermediate for different plastics), was started which involves the anodic condensation of monomethyl adipate CH300C(CH2)4C00 . Dimethyl sebacate is obtained via the scheme of (15.58), and then hydrolyzed in autoclaves to the final product. Methanol is used as a solvent to lower the rates of side reactions. The reaction occurs with current yields attaining 75% and with chemical yields (degrees of utilization of the original adipate) of 82 to 84% (Vassihev et al., 1982). Upon introduction of this process it was no longer necessary to use castor oil, an expensive raw material that was needed to produce sebacic acid by the chemical process. 

Aryloxytitanium halides, 25 83 2-Arylpyridines, 27 111 Aryl phosphate esters, 79 51 Aryl phosphates, 7 7 493 Aryl phosphonates, 79 37 Arylphosphorus compounds, 79 28 Aryls, palladium, 79 652 Aryl-silicon compounds, 22 553, 554 Arylsulfinic acids, 27 248-249 Arylsulfonylated gelatin, 72 444 Aryltin trihalides, 24 810-811 Arylyl amines, 70 396-399 Asahi Chemical Industries EHD processes, 9 676-677 sebacic acid production, 9 679-680 ASAM (alkaline-sulfite-AQ-methanol) process, 27 30... 

Polyamides, commonly known as nylons, may safely be used to produce articles intended for application in processing, handling, and packaging of food, including for products intended to be cooked directly in their packages. Nylon resins are manufactured by condensation of hexyamethylenediamine and adipic acid (nylon 66) or sebacic acid (nylon 610), by the polymerization process, e.g., of co-laurolactam (nylon 12), or by condensation and polymerization, e.g., nylon 66 salts and s-caprolactam. 

In Japan the need for new technology was answered by the development of an electrolytic route to sebacic acid(33). The Kolbe type electrolytic process developed by Asahi involves dimerization of adipic acid half methyl ester salt to give dimethyl sebacate(34). The dimerization proceeds in 92% yield with 90% selectivity based on the adipate half ester. The main drawbacks of this process are the cost of energy utilized by the electrolytic process and the cost of adipic acid. A Chem Systems report indicates a small advantage for the Asahi electrolytic process with ample room for new technology development(35). 

An attractive alternative to building a world scale adipic acid plant is to construct a specialty smaller volume oxycarbonylation plant which is capable of exclusively producing the more valuable precursors for pelargonic and sebacic acid. Oxycarbonylation process conditions can be controlled to give methyl, 4-pentadienoate which is the product from butadiene mono-carbonylation(39,40). Methyl, 4-pentadienoate can react in a subsequent step with butadiene to give an unsaturated pelargonic acid precursor in high yield(41). Methyl, 4-pentadienoate... 

To understand how to control process conditions to give methyl, 4-pentadienoate, the reaction mechanism must be examined. (See Equation 2.). -palladium hydride elimination from 4 gives rise to trans and cis-methyl penta-, 4-dienoate which is the desired monocarbonylation intermediate for sebacic acid. The desired mono-carbonylation reaction is promoted by low carbon monoxide pressure ( 1000 psig) while high pressure (1800 psig) gives excellent 1,4-dicarbonylation product yield. The mono-carbonylation reaction is also facilitated by using a Lewis Acid as a co-catalyst and iodide as the preferred palladium counter-ion (Table III.). Chloride is the preferred palladium counter-ion for 1,4-dicarbonylation. 

More recent developments in this country have included synthesis of relatively stable oils of low volatility, low pour point, and high viscosity index by esterification of octyl alcohols, such as 2-ethylhexanol, with dibasic acids such as adipic acid and sebacic acid (3). Octyl alcohols may be synthesized from petroleum hydrocarbons via the oxo process. Although of relatively high cost, these synthetic oils find general application in making greases for lubrication of antifriction bearings and instruments in aircraft. 

The tendency for ordering on heating near TCN has, up to now, been only demonstrated in the rigid rod-like LCPs. The question that arises is whether such processes could occur in different kinds of morphologies and whether they would have any practical utility. To test this possibility a copolymer of sebacic acid with biphenol and hydroquinone (40/60) was prepared. As can be seen in Fig. 29, such a copolymer could be annealed near 200 °C to produce a more ordered system with a melting point of 240 °C [43], Heating at 260 °C appeared... 

The reaction is illustrated here by the overall conversion of the dicarboxylic acid, sebacic acid, into dodecanedioic acid by a bis-homologation process (Expt 5.130). 

The world-wide production of PA (excluding fibers) in 1997 was 1.6x10 t, with a 75 % use of casting processed materials. For food contact articles the following can be used as starting materials straight chain u -amino acids (C6-C12) and their lactams adipic acids, azelaic acids, sebacic acids, dodecane dicarboxylic acids and heptadecane-dicarboxylic acids salts with hexamethylenediamine isophthalic acid, bis(4-aminocy-clohexyl)-methane, 2,2-bis(4 -aminocyclohexyl)-propane, 3,3 -dimethyl-4,4 -diamino-dicyclohexyl-methane, terephthalic acid or its methylester, l,6-diamino-2,2,4-tri-methylhexane, 1,6-diamino-2,4,4-trimethylhexane, l-amino-3-amino-methyl-3,5,5-tri-methylhexane. 

The dimerization of half esters to l,n-diesters is also called Brown-Walker electrolysis. Thereby valuable intermediates for the synthesis of medium-sized rings or l,n-difunctionalized compounds can be prepared (Table 2, entry 4). This reaction is also of industrial interest since in this way sebacic acid can be prepared from adipic acid half ester. This process has been scaled-up in Germany, the USSR and Japan, and yields as high as 93% have been reported. Reaction conditions and yields for the coupling of other half esters have also been studied in detail. 1, -Polyethylene- or polydifluoromethylene-dicar-boxylic acids are reported to be formed by electrolysis of azelaic acid or perfluoroglutaric acid. Ketocarboxylic acids can be coupled to 1,4-, 1,6- or 1,14-diketones (Table 2, entries 9 and 10). Aldehydes must be dimerized in the form of their acetals to obtain good yields, as has been shown for (17) and (18). The arrow on (10)-(18) indicates the location of dimerization, along with the yield and reaction conditions. 

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