Cyclododecanone 2-

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). 

Dodecanedioic Acid. Dodecanedioic acid (DDDA) is produced commercially by Du Pont ia Victoria, Texas, and by Chemische Werke Hbls ia Germany. The starting material is butadiene which is converted to cyclododecatriene usiag a nickel catalyst. Hydrogenation of the triene gives cyclododecane, which is air oxidized to give cyclododecanone and cyclododecanol. Oxidation of this mixture with nitric acid gives dodecanedioic acid (71). 

To a 3QQ-mL, round-bottomed flask fitted with a water separator, (Note 1) which contains 15 g of Linde 4A molecular sieve l/16-1nch pellets and Is filled with toluene, are added 7.3 g (0.04 mol) of cyclododecanone, 11.4 g (0.16 mol) of pyrrolidine, 100 mL of toluene, and 0.57 g (0.004 mol) of boron trifluoride etherate. The solution is heated under reflux for 20 hr. The water separator is replaced by a distillation head, and about 90 mL of the toluene is removed by distillation at atmospheric pressure. The residue containing l-(N-pyrrolidino)-l-cyclododecene (1) is used in the next step without further purification (Note 2). 

Cycloundecanecarboxylic acid has been prepared by the bromination of cyclododecanone followed by the Favorskii rearrangement of 2-bromocyclo-dodecanone... 

Nylon 12 first beeame available on a semieommercial scale in 1963. The monomer, dodecanelactam, is prepared from butadiene by a multistaged reaction. In one proeess butadiene is treated with a Ziegler-type eatalyst system to yield the cyclic trimer, cyclododeca-1, 5, 9-triene. This may then be hydrogenated to give cyelododeeane, which is then subjeeted to direct air oxidation to give a mixture of cyclododecanol and cyclododecanone. Treatment of the mixture with... 

The reaction of methyl propiolate (82) with acyclic enamines produces acyclic dienamines (100), as was the case with dimethyl acetylenedicarboxylate, and the treatment of the pyrrolidine enamines of cycloheptanone, cyclooctanone, cycloundecanone, and cyclododecanone with methyl propiolate results in ring enlargement products (100,101). When the enamines of cyclohexanone are allowed to react with methyl propiolate, rather anomalous products are formed (100). The pyrrolidine enamine of cyclopentanone forms stable 1,2-cycloaddition adduct 83 with methyl propiolate (82). Adduct 83 rearranges to the simple alkylation product 84 upon standing at room temperature, and heating 83 to about 90° causes ring expansion to 85 (97,100). 

The reaction described is of general synthetic utility for the preparation of a variety of cyclic /3-keto esters from the corresponding ketones. Using this procedure the 2-carbethoxy-cycloalkanones have been prepared from cyclononanone, cyclo-decanone, and cyclododecanone in yields of 85%, 95%, and 90%, respectively. The procedure is simpler and gives much higher yields than other synthetic routes to these systems. 

Cyclododecanone was obtained from Aldrich Chemical Company, Inc. and used without purification. 

Cupric oxide [Copper oxide (CuO)], 10 Cyclodecanone, 111 Cyclododecanone, 108 Cyclododecanone, 2,12-dibromo-, 107 1 -Cy cloheptene, 1 -bromo-7 -acety loxy-[2-Cyclohepten-l-ol, 2-bromo-, acetate], 34... 

Kostichka K, SM Thomas, KJ Gibson, V Nagarajan, Q Cheng (2001) Cloning and characterization of a gene cluster for cyclododecanone oxidation in Rhodococcus ruber SCI. J Bacterial 183 6478-6486. 

Cyclododecanone monooxygenase from Rhodococcus ruber SCI is different from those already mentioned, and is active towards substrates with more than seven carbon atoms (Kostichka et al. 2001). 

Consider an equilibrium-limited esterification reaction. One way to drive the reaction to completion is to remove the water formed by the reaction selectively through a membrane. This can be an attractive strategy when higher temperatures are undesirable due to factors like colouration of the materials and formation of undesirable products even though these may be present at a low level. As another example, consider the air oxidation of cyclohexane or cyclododecane to cyclohexanone/-ol or cyclododecanone/-ol, where the product can undergo more facile oxidation to unwanted or much lower value products. Consequently, industrial processes operate at a level of less than 5% conversion. If a membrane can selectively remove cyclohexanone as it is formed, the problems mentioned above can be thwarted. However, selective polymeric membranes, which can work at oxidation temperature, have not yet been proved. 

Methallyl chloride 1-Propene, 3-chloro-2-methyl- (8,9) (563-47-3) 2-(Hydroxymethylene)cyclododecanone Cyclododecanone, 2-(hydroxymethylene)-(9) (949-07-5)... 

In a separate, dry, 1-L, two-necked, round-bottomed flask fitted to a nitrogen bubbler and equipped with a magnetic stirring bar and a septum inlet is added a solution of 12.6 g (60.0 mmol) of 2-(hydroxymethylene)cyclododecanone (Note 4) in 500 mL of anhydrous ether. The stirred ethereal solution of the hydroxymethylene ketone is treated at 22°C with 33 mL of a freshly prepared mixture (1/1, v/v) of chlorotrimethylsilane and triethylamine (Note 5). An immediate reaction takes place with deposition of a white precipitate. The mixture is stirred thoroughly at 22°C for 15 min to insure complete conversion to the silyl enol ether. 

Cyclododecanone is reduced to a mixture of cis- and /ra .s -cyclododecenc in high yield with trimethylsilane and tetrakis-3,5-bis(trifluoromethylphenyl)borate (TFPB, 77) (Eq. 254).424... 

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%. 

VG Bykovchenko. Kinetics and Mechanism of Cyclododecane Oxidation Directed to Hydroperoxide and Cyclododecanone. Ph.D. thesis, Moscow State University, Moscow, 1962, pp. 3-11 [in Russian]. 

The same reaction sequence may be used to convert cyclo-dodecanone to cyclotetradecanone. Preparation of the pyrrolidine enamine of cyclododecanone requires 2-3 days at reflux, and reaction of the enamine with methyl propiolate is best carried out in refluxing hexane. The enamine-propiolate reaction may also be used to convert cycloheptanone to cyclononanone. In this case the procedure must be modified to provide for partial hydrogenation of the intermediate amino ester without prior hydrolysis.8 The reduced intermediate is saponified as described in the present procedure. 

Cyclobutanecarboxylic acid, reaction with hydrazoic add, 47, 28 Cyclobutene, 1,2,3,4-tetramethyl-3,-4-oichloro-, 46, 34 reactions of, 46, 36 Cyclobutylamine, 47,28 Cvclobutyl isocyanide, 46, 77 Cyclodecanone, 48, 56 Cyclododecanone, conversion to cyclo-tetradecanone, 48, 58 Cyclohcptanone, 45, 31 conversion to cyclononanone, 48, 58 1, 3-Cyclohexadiene, 47, 31... 

This hypoiodite reaction can also be used for ring expansion of cyclic ketones.2 Thus Barbier cyclization of a-(w-iodopropyl)cyclododecanone (3) furnishes the bicyclic alcohol 4, which undergoes regioselective cleavage to a 15-membered iodo... 

Thioanisolc. A system utilizing thio-anisole as an organic mediator was developed for the oxidation of secondary alcohols to ketones (Fig. 5 2-octanol to 2-octanone 99%, menthol to menthone 92%, cyclododecanol to cyclododecanone 75%) [43]. The use of 2,2,2-trifluoroethanol as a solvent in the mediatory system improved the yields [44]. 

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