Dodecane derivatives

The reaction of perfluorobicyclobutylidene with buta-1,3-diene required a temperature of 80 °C to occur, giving the dispiro[3.0.3.4]dodecane derivative 5.79... 

Of the four non-propellane members of the tetraquinane family, one is a dodecane derivative 482), one is composed of thirteen carbon atoms (483), and two are tetra-decanes (484 and 485). Chemistry relating to these systems is just beginning to evolve and future developments in this area are awaited. 

Change of configuration around the C(2)-C(3) bond was found in some nucleophilic substitution reactions of aminobicyclo[9.1.0]dodecane derivatives (515) (equation 133). The isomerization was assumed to take place at the stage of an aminoally cation, which is in equilibrium with a bicyclic iminium ion (see also equations 95 and 96). 

The cis or trans configuration of the annulated system normally is not changed in nucleophilic substitution. Such a cisitrans isomerization, however, has been observed in a few nucleophilic substitution reactions of various bicyclo[9.1.0]dodecane derivatives. ... 

Phosphane-free palladium(O) catalysts convert 3,3-dialkylcyclopropenes to tram-. x -cyclo[3.1.0.0 ]hexane derivatives 16 as the major product together with pentacy-clo[9.1.0.0 . 0 . 0 ]dodecane derivatives (12-16%). In the presence of phosphanes, the tetracyclo[6.1.0.0 . 0 ]nonane systems 17 was formed in > 80% yield. ... 

The reaction took a different course when an electron-deficient alkene or alkyne was used as the reaction partner. In that case, the first diradical, i.e. the spirocyclohexadienylethyl diradical (8), was trapped to afford dispiro[2.2.4.2]dodecane derivatives 16,17. ° More complex product mixtures were obtained when alkenes with alkyl substituents, e.g. 3,3-dimethylbut-l-ene, were used in this reaction. ... 

Photoreactions of Thymines etc. - The uracil derivative (184) undergoes photochemical transformation when it is irradiated in frozen benzene with added trifluoroacetic acid. Cyclodimerization occurs yielding derivatives of diaza-pentacyclo[6.4.0.0 . 0 . 0 ]dodecane derivatives such as (185). Other addition products (186) and (187) were also identified. The photoreduction of 5-bromo-uracil (188) has been studied. ... 

Reaction of 2,6-dimethyl-l,4-benzoquinone with the quinomethyl carbanion derived from 2,3-dimethyl-1,4-naphthoquinone is reported to give the tricyclo-[6,3,l,0 ]dodecane derivative (749). Pyrolysis of the sodium salt of the tosyl-hydrazone of 7-cycloheptatrienylmethyl methyl ketone in diglyme at 150 C afforded (750 7%) similar pyrolysis of the tosylhydrazone salt from l-(7-cycloheptatrienyl)-ethyl methyl ketone gave (751 9 %). Both compounds are examples of the previously... 

Although the synthesis or the detection of the tautomer of the simple cyclooctapyrimidine (2a) derived from la was unsuccessful, photolysis of 6-ClDMU in frozen benzene (-25°C) in the presence of TFA resulted in the formation of pentalenopyrimidine derivatives (16ai, ii, iii) and a diazapentacy-clo[6.4.0.0 . 0 .0 > ]dodecane derivative (12a) in moderate yields (Scheme 14). These results indicate that the tautomer (7a) maybe involved in the present reaction as the key intermediate. 

Bohlmann et al. (118-121) observed that an infrared absorption band between 2700-2800 cm is characteristic of a piperidine derivative possessing at least two axial carbon-hydrogen bonds in antiperiplanar position to the free-electron pair on the nitrogen atom. The possibility of forming an enamine by dehydrogenation can be determined by this test. Compounds which do not fulfill this condition cannot usually be dehydrogenated (50, 122,123). Thus, for example, yohimbine can be dehydrogenated by mercuric acetate,whereas reserpine or pseudoyohimbine do not react (124). The quinolizidine (125) enamines (Scheme 4), l-azabicyclo(4,3,0)-nonane, l-azabicyclo(5,3,0)decane, l-azabicyclo(5,4,0)undecane, and l-azabicyclo(5,5,0)dodecane have been prepared in this manner (112,126). 

Mass transfer for this technique was examined by studying the protonation and aggregation kinetics of 5,10,15,20-tetraphenylporphyrin (H2TTP) at the dodecane-aqu-eous interface [61]. The rate law for the diffusion-controlled protonation of H2TTP at the interface was derived. 

Murthy. K. S. Zografi, G., Oil-water partitioning of chlorpromazine and other phenothiazine derivatives using dodecane and n-octanol, J. Pharm. Sci. 59, 1281-1285 (1970). 

In obtaining Fig. 18, it has been assumed that the complexation between a-CD and OE follows the 3 1 stoichiometry independently of the mixing ratio of the two components. In fact, XH NMR spectra of the isolated complexes confirmed this assumption, and furthermore, the complexation of a-CD with such derivatives of OE(6) (dodecane) as a,co-diaminohexaethylene, a,co-dihyd-roxyhexaethylene, and a,co-dicarboxyhexaethylene was found to obey the 3 1 stoichiometry. 

The systems discussed up to now all showed chiral susceptibilities that were of the same order of magnitude or smaller than the achiral susceptibility components. The system that we discuss in this section has chiral susceptibilities that dominate the nonlinear optical response.53 The material is a chiral helicenebisquinone derivative shown in Figure 9.22. In bulk samples, the nonracemic, but not the racemic, form of the material spontaneously organizes into long fibers clearly visible under an optical microscope. These fibers comprise columnar stacks of helicene molecules.54,55 Similar columnar stacks self-assemble in appropriate solvents, such as n-dodecane, when the concentration exceeds 1 mM. This association can be observed by a large increase in the circular dichroism (CD) of the solutions. 

REDUCTION OF ALKYL HALIDES AND TOSYLATES WITH SODIUM CYANOBOROHYDRIDE IN HEXAMETHYL-PHOSPHORAMIDE (HMPA) A. 1-IODODECANE TO n—DECANE B. 1-DODECYL TOSYLATE TO n-DODECANE, 53, 107 REDUCTION OF KETONES BY USE OF TOSYLHYDRAZONE DERIVATIVES ANDROSTAN-17 0—OL, 52, 122 REDUCTIVE AMINATION WITH SO-... 

In activated sludge, 80.6% degraded after a 47-h time period (Pal et al., 1980). Chemical/Physical. Zhang and Rusling (1993) evaluated the bicontinuous microemulsion of surfactant/oil/water as a medium for the dechlorination of polychlorinated biphenyls by electrochemical catalytic reduction. The microemulsion (20 mL) contained didodecyldi-methylammonium bromide, dodecane, and water at 21, 57, and 22 wt %, respectively. The catalyst used was zinc phthalocyanine (2.5 nM). When PCB-1221 (72 mg), the emulsion and catalyst were subjected to a current of mA/cm on 11.2 cm lead electrode for 10 h, a dechlorination yield of 99% was achieved. Reaction products included a monochlorobiphenyl (0.9 mg), biphenyl, and reduced alkylbenzene derivatives. 

There are two general systems of nomenclature for fatty acids, as well as a few useful shorthand designations. Common names have their origins in history and are frequently used. Several examples are provided in table 18.1. Systematic names derive from the number of carbon atoms in the fatty acid for example, lauric acid is systematically known as dodecanoic acid. The parent hydrocarbon dodecane has 12 carbon atoms as does lauric acid. Several other examples are provided in table 18.1. 

The A,A A"-tris(carboxymethyl) derivative of the 12-membered macrocycle 1,5,9-triazacyclo-dodecane yields a complex of type [MnL] in aqueous solution which is approximately two orders of magnitude less stable than the corresponding complex of l,4,7-tris(carboxymethyl)-1,4,7-triazacyclononane, as might be expected for the substitution of three six-membered chelate rings in the former for three five-membered chelate rings in the latter. " ... 

Both single and double cyclizations of the Schiff bases 65A and 66A occur in the multicomponent tautomeric mixtures derived from as- and /ra t-cyclohexane aminodiols 69 and 70, to give monocyclized ring forms of C-2-epimeric perhydro-l,3-benzoxazines (B and G) and oxazolidines (D and E), besides 7,ll-dioxa-9-azatricyclo[7.2.1.0 °]-dodecane diastereomers 67 and 68 (Scheme 10). The tautomeric ratios are found to satisfy by Equation (1) (Table 1) and are influenced by the cis- or rra t-geometry of the cyclohexane substituents in the Schiff base (A). For the equilibria... 

Base-catalyzed retro-aldolization of a protected 10-hydroxybicyclo[8.2.0]dodecane-l-carboxy-late 2 afforded a bridged cyclododecanone derivative 3.14... 

The first PGSE investigation of a rubber-based ternary solution was described by Ferguson and von Meerwall31), who measured diffusion of C6F6(19F NMR) and n-paraffin (n-dodecane or n-hexatriacontane 1H NMR) in a commercial polybutadiene as function of both concentrations. They showed that both concentration dependences in the ternary region can be derived from the measured diffusivity of each diluent i = 1, 2 in binary solution in the rubber. To do this it was necessary to extend the Fujita-Doolittle expression, as follows ... 

The synthesis illustrates several important types of reactions that we have discussed in this and previous chapters. First, the alkyl group R usually is a C12 group derived from the straight-chain hydrocarbon, dodecane, which on photochlorination gives a mixture of chlorododecanes ... 

Y. Sasaki, Y. Sugo, S. Suzuki, and T. Kimura. A method for the determination of extraction capacity and its application to N,N,N, N -tetraalkyl derivatives of diglycol-amide-monoamide/n-dodecane media. Anal. Chim. Acta, 543(1-2) 31—37, 2005. 

M 54] [P 49] A validation of the volume-tracking method, applied for droplet simulation, was performed by comparing the simulated equivalent diameters of droplets with data derived from analytical correlations [135], Assuming a nozzle diameter of 1 mm and taking water and dodecane as dispersing and continuous... 

Some other reaction courses were also seen. For example, 3a, R=octyl with butyllithium gave no significant yield of dodecane. The 31P chemical shift of an important component suggested an ylide, perhaps derived from butyltriphenylphosphonium from attack at P rather than C. Ethyl magnesium bromide with 3a, R=octyl gave mostly 1-bromooctane, but with butylmagnesium chloride, about 20% yield of dodecane was observed with no 1-chlorooctane. 

Therefore, another strategy was developed, based on the induced-fit concept, which uses flexible receptors in order to optimize the interactions between the donor atoms and the metal ion. In fact, the coordination environment is built upon complexation thanks to the flexibility introduced into the complexation agent, which is now termed predisposed ligand . These receptors are either large macrocycles able to wrap around the guest or small macrocycles fitted with pendant arms. The latter approach has proved to be very successful, particularly with calixarene (Asfari et al., 2001) and cyclen (1,4,7,10-tetraaza-dodecane) (Lukes et al., 2001) derivatives. 

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