Undecane-, sodium

Triketone (57), a key intermediate in the synthesis of 4,4,7,7,11,11-hexanitropentacyclo [6.3.0.0 .0 °.0 ]undecane (61) (Zlj-hexanitrotrishomocubane), has been synthesized independently by both Marchand and co-workers, and Fessner and Prinzach. Marchand and co-workers prepared the trioxime (58) from the corresponding triketone (57). Oxidation of (58) with peroxytrifluoroacetic acid in acetonitrile provides a direct route to the trinitro derivative (59) in 35 % yield, this yield reflecting an efficiency of 70 % for the oxidation of each oxime group. Subsequent oxidative nitration of (59) with sodium nitrite and potassium ferricyanide in aqueous sodium hydroxide yields the target T>3-hexanitrotrishomocubane (61). 

Marchand and co-workers have provided synthetic routes to both 8,8,11,11 -tetranitro- (72) and4,4,8,8,11,11-hexanitro- (80) pentacyclo[5.4.0.0 .0 °.0 ]undecanes. Initial attempts to synthesize target (72) from the dioxime (63) failed when it was found that sodium boro-hydride reduction of the gm-bromonitro intermediate (64) gave the aza-heterocycle (65) as the major product. Consequently, an indirect route was explored where one of the two ketone groups of (62) is protected as an acetal (66) while the other ketone group is converted to a... 

Manxine (l-azabicyclo[3.3.3]undecane 60) is an interesting compound which can be prepared in 60% yield by reduction of the quaternary ammonium salt (59) with sodium in liquid ammonia. It has a melting point of 150-152 °C and a remarkably long wavelength absorption [Amax 240 nm, e 2935 (ether)] for a saturated amine. Its pKa (9.9) is one unit... 

The tricyclic compound 3-methoxytricyclo[5.4.0.02-8]undecan-9-one (21) was conveniently prepared in 91 % yield by treating 2-bromo-3-methoxybicyclo[5.4.0]undecan-9-one with sodium hydride in dimethyl sulfoxide.20... 

Thioxo-6,7,9-triazaspiro[4.5]decan-10-one (714a) and 3-thioxo-l,2,4-triaza-spiro[5.5]undecan-5-one (714b) were obtained when the l-(l-thiosemicarbazido)cyclo-alkanecarboxamides (713) were treated with sodium ethoxide (63FRP1324339). 

An alternative procedure is to convert the carbonyl compound into the toluene-p-sulphonylhydrazone,12 followed by reduction with either sodium borohydride in acetic acid,13 or with catecholborane, followed by decomposition of the intermediate with sodium acetate or tetrabutylammonium acetate.14 The former method is illustrated by the conversion of undecan-6-one into undecane (Expt 5.6), and the latter by the conversion of acetophenone into ethylbenzene (Expt 6.4, Method B). A feature of these methods is that with a, / -unsaturated ketones, migration of the carbon-carbon multiple bond occurs thus the tosylhydrazone of isophorone gives 3,3,5-trimethylcyclohex-l-ene, and the tosylhydrazone of oct-3-yn-2-one gives octa-2,3-diene. 

To a slurry of undecan-6-one toluene-p-sulphonylhydrazone (5.08 g, 15 mmol) (1) in 50 ml of glacial acetic acid is added sodium borohydride pellets (c. 5.67 g, 150 mmol, 24 pellets) (2) at such a rate that foaming is not a problem (c. 1 hour). The solution is stirred at room temperature for 1 hour and then at 70 °C for 1.5 hours. The solution is then poured into crushed ice, made basic with aqueous sodium hydroxide and extracted with three portions of pentane. The pentane solution is dried and concentrated in a rotary evaporator, and the residue distilled at reduced pressure (Kugelrohr apparatus) to obtain 1.96 g (84%) of undecane. Undecane has b.p. 87 °C/20 mmHg. 

General procedure for the preparation of oxathiolanes.140 To a stirred refluxing solution of cycloheptanone (56.1 g, 0.5 mol) and 2-mercaptoethanol (29.1 g, 0.5 mol) in anhydrous ether (400 ml) was added dropwise over a 1-hour period boron trifluoride-etherate (71 g, 0.5 mol). After an additional hour of being heated under reflux, the solution was allowed to cool, washed with 0.1 m sodium hydrogen carbonate solution (2 x 100 ml) and once with saturated sodium chloride solution (100 ml), and dried over magnesium sulphate. After removal of the solvent under vacuum on a rotary evaporator, the residue was distilled under vacuum to yield a small forerun which was followed by 2-oxa-5-thiaspiro[4.6]undecane (79.2g, 92%), b.p. 77-78°C/1.2mmHg, n 5 1.5165. 

In all isotherms plotted within the region of low surfactant concentrations (2.5 10 6 to 3 I O 6 mol dm 3) and at A a - 0.5 mN m l there is a linear part corresponding to r = kC dependence (r is the adsorption). This part of the isotherm for curve 1 is presented in linear co-ordinates on the top left side of Fig. 3.77. A short plateau follows where dAo/d gC = 0. The further increase in surfactant concentration leads to a parabolic increase in Act until the next flexion of the curve is reached at Act - 8-10 mN m 1. Similar change in the course of Ao(0 isotherms has been found also for potassium and sodium oleates solutions [369,370], decane and undecane acid solutions [366] and aqueous solutions of saturated fatty alcohols [367]. It is worth to note that the measurements were carried out with purified substances so that any inoculations by a second surfactant are excluded. With the increase in surfactant concentration the parabolic part gradually transforms into a second linear part of the isotherm. 

A 500-ml Erlenmeyer flask was charged withl,5-dioxa-9-aza-8,8,10,10-tetramethyl-spiro [5,5]-undecane (0.04 mole) dissolved in 150 ml of methanol and then treated with 40 ml of 35% aqueous hydrogen peroxide followed by sodium tungstate dehydrate (0.4 g). The mixture was left for 3 days at ambient temperature where after one day the color became dark orange. It was then extracted with three 50-mI portions of t-butyl methyl ether and dried with an anhydrous Na2S04. The solution was concentrated, and... 

Mercuriocyclization has also been utilized in order to obtain spiroketals from hemiketals. Thus, treatment of l,10-undecadien-6-one (11) with mercury(II) acetate in water/tetrahydrofuran affords, with total regioselectivity, 2,8-bis[(chloromercurio)mcthyl]-l,7-dioxaspiro[5.5]undccanc as a diastereomeric mixture. The diastereomeric ratio was not reported but depends on the reaction time, owing to the reversibility of oxymercuration-cyclization steps. Reductive removal of mercury by sodium borohydride under phase-transfer conditions gives a good yield of 2,8-dimethyl-l,7-dioxaspiro[5.5]undecane (12) as a diastereomeric mixture101,102. 

Hydrolysis of the 10-chloro derivative 36 in 0.5 M sodium hydroxide solution at 50°C for 6 hr gave the 2,6-diazabicyclo[5.4.0]undecan-l-one (39), probably via the 11-membered azalactam (38) through intramolecular alkylation (84JHC583). 

Cyclopropyl trialkylsilyl ethers are readily converted to the corresponding cyclopropanols, in most cases in very good yield. A range of reaction conditions have been utilized dry methanol, methanol and hydrochloric acid, aqueous sodium hydroxide, or potassium fluoride, hydrochloric acid in diethyl ether or tetrahydrofuran, and tetrabutylam-monium fluoride in tetrahydrofuran ammonium chloride has also been used. Some compounds are sensitive to the reaction conditions. Thus, (l/ , 3S, 75 )-3-(/( r/-butyldimethyl-siloxy)tricyclo[5.4.0.0 ]undecane (6) reacted with aqueous hydrochloric acid in diethyl ether without strictly excluding oxygen to give (l/ , 65, 105 )-ll,12-dioxatricyclo[8.2.1.0 ]tri-decan-10-ol (7) in variable yield in addition to (17 , 65, 105 )-l-methylbicyclo[4.4.0]undecan-2-one. ... 

Mercury(II) acetate also underwent addition across this particular bond of 9 and gave endo-tetracyclo[5.3.1,0 .0 ]undecan-3-ol (12) in excellent yield following the reduction of the primary adduct with sodium borohydride. The enrfo-product suggests the intervention of a 1,3-bridged metal ion in these reactions. 

For solutions of typical ionic surfactants with no added salts the studies of Carroll and Ward showed that solubihzation rates were much smaller than those for nonionic surfactants, presumably because the surfactant ions adsorbed at the oil-water interface repelled the micelles of like charge in the solution. Indeed, Bolsman et al. found no measurable solubilization of n-hexadecane into solutions of a pure benzene sulfonate and a commercial xylene sulfonate. They injected small oil drops into the surfactant solutions and observed whether the resulting turbidity disappeared over time due to solubilization. Similarly, Kabalnov found from Ostwald ripening experiments that the rate of solubilization of undecane into solutions of pure SDS was independent of surfactant concentration and about the same as the rate in the absence of surfactant. That is, the hydrocarbon presumably left the bulk oil phase in this system by dissolving in virtually miceUe-free water near the interface. In similar experiments TayloC and Soma and Papadopoulos observed a small increase in the solubilization rate of decane with increasing SDS concentration. De Smet et al., who used sodium dodecyl benzene sulfonate, which does not hydrolyze, found, like Kabalnov, a minimal effect of surfactant concentration. 

Precision of Measurements. Aliquots from a stock solution of 0.1 M sodium oleate (five months old) were used to prepare aqueous test solutions that were 0.01 M in sodium oleate and 0.1 M in sodium chloride pH 9 5 Interfacial tensions were measured against n-undecane without pre-equilibration. The second solution was made and measured one week after the first and the third solution two weeks after the first. The results in Table I... 

Precision of Interfacial Tension Measurements 0.01 M Sodium Oleate, 0.1 M Sodium Chloride pH 9 5 vs n-Undecane... 

Effect of Sodium Chloride Concentration. Figure b compares interfacial tensions of several different surfactant concentrations verses n-undecane in the presence of 0.1 M sodium chloride with values obtained without salt. Salt reduces the interfacial tension at all surfactant concentrations. Aqueous potassium oleate has a critical micelle concentration of 0.001 M (13). It could be inferred from Figure b that 0.001 M sodium oleate with no added salt is below the cmc, because of the high interfacial tension. If so, the much lower interfacial tension in the presence of 0.1 M sodium chloride stems from reduction of the cmc expected in the presence of added salt (lb). 

The reaction of a silicon substituted malonic ester with urea in the presence of sodium ethoxide affords the 3-oxa-8,10-diaza-2,4-disilaspiro[5.5]undecan-9-one (58) <81MI 627-04>. 

High yields of cyclobutane derivatives are obtained from the bis-p-toluene-sulfonates of 1,3-diols, as is shown by the synthesis of diethyl dispiro[3.1.4.1 ]-undecane-2,2-dicarboxylate from 2,2-spiro [3,4]octanebis(methyl /7-toluene-sulfonate) and ethyl malonate (warming with sodium in xylene) 386... 

C. fi-Oxido ) annulene. A 2-1., three-necked, round-bottomed flask equipped with a sealed mechanical stirrer and a reflux condenser protected by a calcium chloride drying tube is charged with 81 g. (1.5 moles) of sodium methoxide (Note 9) and 600 ml. of anhydrous ether. To this slurry is added, with stirring, 117 g, (0.25 mole) of flnely powdered 3,4,8,9-tetrabromo-ll-oxatricyclo[4.4.1.0 - ]undecane. The reaction mixture is refluxed with stirring for 10 hours and is then allowed to stand overnight. Following this, 500 ml. of water is added slowly to dissolve the solids. The ether layer is separated and the aqueous layer is extracted with two 100-ml. portions of ether. The combined ethereal solution is washed with 250 ml. of water and dried over anhydrous potassium carbonate. Removal of the ether under reduced pressure on a rotary evaporator affords a brown oil that is distilled to give 34.4-35.1 g. of yellow l,0-oxido[10]annulene, b.p. 77° (0.02 mm.) (Note 10). This material readily solidifies at room temperature. After two recrystallizations at —40° from 225-ml. portions of pentane-ether (5 1), 18.3-18.5 g. (51%) of l,6-oxido[10]annulene is obtained as pale yellow needles, m.p. 51-52° (Notes 11 and 12). 

Sodium perchiorate monohydrate n-Undecane fuei, jet engines Kerosene... 

Octyl acrylate Periodic acid Phenylhydrazine Propylcyclohexane Propylcyclopentane Sodium persulfate 1,1,2,2-Tetrachloroethane 1,3,5-Trichlorobenzene 2,2,3-Trimethyl butane 1,1,2-Trimethylcyclopentane 1,1,3-Trimethylcyclopentane n-Undecane Xylidine... 

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