Oximation of cyclododecanone

Table 1115 lists some economic data concerning the processes lor manufacturing laurolactam by the oximation of cyclododecanone and by the photomtrozation of cydo-dodecane. 

Table 23.2 Rates of oximation of cyclododecanone in the presence of microparticles of carbon (from Janakiraman and Sharma, 1985)... 

The solid-liquid alkaline hydrolysis of esters such as phenyl benzoate, ethyl p-nitrobenzoate and 2,4-dichlorophenylbenzoate has been studied in the presence of sodium p-toluene sulfonate, sodium xylene sulfonate and the sodium salts of phenol, p-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol. The solubilities of the esters in water is very low, but in the presence of the hydrotropes considerably higher reaction rates are obtained due to higher solubilities (30). The same behaviour was observed by using urea in the solid-liquid oximation of cyclododecanone where the reaction rate was increased. From studies of these types of reactions, the following observations were made (31) ... 

Pandit. A. and Sharma, M. M., Intensification of heterogeneous reactions through hydrotropy alkaline hydrolysis of esters and oximation of cyclododecanone, Chem. Eng. ScL, 42, 2517-2523 (1987). 

To a stirred solution of cyclododecanone oxime (1 mmol) in EtOH (10 mL) were added PMHS (180 mg, 3.0 mmol), di-ferf-butyl dicarbonate (240 mg, 1.1 mmol), and 10% Pd/C (10 mg). The reaction mixture was stirred at 40-50° for 7 hours, after which time it was filtered and the filtrate concentrated under vacuum. The crude product was purified by column chromatography to give N-Boc-cyclododecylamine 80%. 

A stirred mixture of 10 gm (0.05 mole) of nitrosocyclododecane and 10.1 gm (0.051 mole) of cyclododecanone oxime in 100 ml of propionic acid is heated to reflux for 3 hr. Then the reaction mixture is distilled under reduced pressure to... 

The reaction of ammoximation is generally apphcable and provides an efficient route to many other oximes in addition to the industrially relevant cyclohexanone oxime. Acetone, butanone, acetophenone, C5—Cg cycUc ketones and methyl-substituted cyclohexanones produced the corresponding oximes with high conversion and selectivity. Even the ammoximation of cyclododecanone and 4-butylcyclohexa-none, unable to diffuse in TS-1, occurred with high yields [121-123]. Other ammo-ximation catalysts are carbon-supported TS-1, TS-2, Ti-MOR and Ti-MWW, with conversions and selectivities close to those of TS-1 [124—128]. 

In this case, the conversion of cyclododecanone and cyclooctanone oxime were done by the Beckman rearrangement in liquid phase, in a batch reactor at 403 and 433 K, respectively, with a catalyst to oxime ratio of 1 2 wt.wf, and chlorobenzene and sulfolane as solvent, respectively. The results reported in Table 5 show a higher activity for the delaminated ITQ-2 sample. Moreover, adsorbed products are easier to be removed from the surface of the delaminated material, as indicated by the smaller amount of organic left on the solid after reaction which was in the case of cyclododecanone-oxime, 2, 3 and 5 wt% for ITQ-2, MCM-41 and Beta, respectively. By optimising temperature and solvent, conversions higher than 95% with selectivities to the lactames > 98% can be obtained with ITQ-2. 

Oximation of cyclododecane, a solid-liquid reaction, was studied by Janakiraman and Sharma (1985) by reacting finely ground particles of cyclododecanone (CD) with aqueous hydroxylamine sulfate (HAS) in a mechanically agitated contactor, with and without microparticles of carbon. The carbon particles are not catalysts but strongly adsorb the solid reactant (which is otherwise only sparingly soluble in the aqueous phase) and transport it to the aqueous bulk, where reaction occurs at an enhanced rate. The reaction was carried out at 2 °C, at an agitator speed of 1200 rpm, and a ketone holdup of 0.04 g/cm. Carbon microparticles of two sizes, 1.7 p and 4.33 p, were used, and volumetric rates (mol/scm aqueous phase) were determined at different microphase loadings for each size. These are presented in Table 23.2. 

An oxidative cleavage of cycloalkanones to unsaturated aldehyde-esters has been developed. Thus, for example, cyclononanone was converted into 2,2-dithio-trimethylenecyclononanone, which was cleaved using lead(iv) acetate (66 %), and the product so obtained treated with methanol and sodium periodate to give (208 in = 5). Cyclododecanone was similarly converted into (208 n = 8). 1,2-Bis(trimethyl-silyloxy)cycloalkenes, prepared by acyloin condensations, have been converted into 2-alkyl-2-hydroxycycloalkanones by treatment with methyl-lithium and an alkyl halide, and the oximes of these a-hydroxyketones cleaved to give open-chain co-cyanoketones using mesyl chloride-pyridine. ... 

The rearrangement of cyclododecanone oxime 42 to laurolactam 43 has been achieved in the presence of siliceous and Al-containing MFI-type zeolites. ... 

The production of ft -laurolactam by Beckmann rearrangement of cyclododecanone oxime on a sohd acid catalyst in the vapor phase was reported in [155]. The acid-treated [A1,B]-BEA zeohte at 320°C and reduced pressures demonstrates the complete conversion combined with the excellent selectivity of 98%. 

Nylon-12. Laurolactam [947-04-6] is the usual commercial monomer for nylon-12 [24937-16-4] manufacture. Its production begins with the mixture of cyclododecanol and cyclododecanone which is formed in the production of dodecanedioic acid starting from butadiene. The mixture is then converted quantitatively to cyclododecanone via dehydrogenation of the alcohol at 230—245°C and atmospheric pressure. The conversion to the lactam by the rearrangement of the oxime is similar to that for caprolactam manufacture. There are several other, less widely used commercial routes to laurolactam (171). 

Cyclic ketones are suitable starting material for the preparation of corresponding oximes and dicarbonic acids, which are key intermediates for the production of various types of nylons. Recently, BASF announced [176] the development of a new process for cyclododecanone production via the ketonization of cyclododecene (entry 4, Table 7.9), for which commercialization is expected in 2009. 

Trapping of the Beckmann intermediates with enol silyl ethers affords facile entry to a variety of en-amino ketones. This condensation takes place with retention of regiochemical integrity in both oxime sulfonates and enol silyl ethers. Reaction of 6-methyl-l-(trimethylsiloxy)-l-cyclohexene (41) or 1-methyl-2-(trimethylsiloxy)-l-cyclohexene (42) with cyclohexanone oxime mesylate furnishes (43) or (44), respectively, as the sole isolable products (equation 25). Another striking feature of the reaction is the high chemospecificity. The condensation of the enol silyl ether (45), derived from p-acetoxyaceto-phenone, occurs in a chemospecific fashion with cyclododecanone oxime mesylate, the acetoxy moiety remaining intact (equation 26). Oxime sulfonates of aromatic ketones and cyclopentanones are not employable since complex reaction mixtures are formed. 

The TS-1 catalyzed hydroxylation of phenol to a 1 1 mixUne of catechol and hydroquinone has been commercialized by Enichem. Similarly, the ammoximation of cyclohexanone is being developed commercially as a low-salt alternative to the conventional process for the production of cyclohexanone oxime, the raw material for nylon-6. The reaction involves initial TS-1 catalyzed oxidation of NH3 by HjOj to give NH2OH. The fact that bulky ketones such as cyclododecanone undergo ammoximation is consistent with subsequent reaction of NHjOH with the ketone substrate taking place outside the molecular sieve. The method has been used [49] for the conversion of p-hydroxyacetophenone to the corresponding oxime which is the precursor of the analgesic paracetamol (Reaction 13). 

It was very recently reported that cyclododecanone oxime was converted to its corresponding lactam by Cs2,5f/o.5PWi204o catalyst, the activity of which was much higher than that of either Amberlyst or Nafion-Si02. The reaction proceeded at 373 K, indicating it occun ed as solid-solid reactions [64],... 

Synthesis of the lactames of cyclooctanone and cyclododecanone oxime at 430 C and 90 minutes reaction time on various catalyst with a Si/Al ratio of 50. 

The CDT is then hydrogenated and further oxidized at 150°C to cyclododecanol and cyclododecanone with oxygen from the air. In this reaction, up to 5% ketone hydroperoxide occurs, which can be decomposed to form cyclododecanol, cyclododecanone, and dicarboxylic acid. These undesired reactions can be prevented by adding boric acid, which is present as polyboric acid at this temperature. The peroxide probably forms an adduct with the polyboric acid, and the course of this reaction is not yet fully understood. The cyclododecanone is changed to lauryl lactam via the oxime in the usual way (cf. nylon 6). 

Analysis Weigh the flask and calculate the yield of solid cyclododecanone. Determine the melting point of the product. Prepare the semicarbazone (mp 218-219 °C) or oxime (mp 131-132 °C) according to the procedures given in Sections 25.7G and 25.7H. If necessary, recrystallize the derivatives from methanol. Obtain IR and NMR spectra of your starting material and product, and compare them with those of authentic samples (Figs. 16.1-16.4). 

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