Alkanes coupling with

Figure 2.6 Gas cluotnatograni of a 10 ml test sample containing C I4 C26 alkanes in -hexane (about 1 ppb each) the earner gas (H2) inlet pressure was 2.5 bar for a 22 m X 0.32 mm id separation column coupled with a 2 m X 0.32 mm id uncoated precolumn (no vapour exit). Reprinted from Journal of High Resolution Chromatography, 9, K. Grob et al., Concunent solvent evaporation for on-line coupled HPLC-HRGC , pp. 95-101, 1986, with peimission from Wiley-VCH.

Haloalkynes (R—C=C—X) react with ArSnBu3 and Cul to give R—C= C—Ar. Acetylene reacts with two equivalents of iodobenzene, in the presence of a palladium catalyst and Cul, to give 1,2-diphenylethyne. 1-Trialkylsilyl alkynes react with 1-haloalkynes, in the presence of a CuCl catalyst, to give diynes and with aryl triflates to give 1-aryl alkynes. Alkynes couple with alkyl halides in the presence of Sml2/Sm. Alkynes react with hypervalent iodine compounds " and with reactive alkanes such as adamantane in the presence of AIBN. ... 

The use of tetraoctylammonium salt as phase transfer reagent has been introduced by Brust [199] for the preparation of gold colloids in the size domain of 1-3 nm. This one-step method consists of a two-phase reduction coupled with ion extraction and self-assembly using mono-layers of alkane thiols. The two-phase redox reaction controls the growth of the metallic nuclei via the simultaneous attachment of self-assembled thiol monolayers on the growing clusters. The overall reaction is summarized in Equation (5). 

In aqueous DMF, the reaction can be applied to the formation of C-C bonds in a solid-phase synthesis with resin-bound iodobenzoates (Eq. 6.33).80 The reaction proceeds smoothly and leads to moderate to high yield of product under mild conditions. The optimal conditions involve the use of 9 1 mixture of DMF-water. Parsons investigated the viability of the aqueous Heck reactions under superheated conditions.81 A series of aromatic halides were coupled with styrenes under these conditions. The reaction proceeded to approximately the same degree at 400°C as at 260°C. Some 1,2-substituted alkanes can be used as alkene equivalents for the high-temperature Heck-type reaction in water.82... 

These new data acquired with double-labeled vinyl probes (13CH2=13CHBr and 13CH2=13CH2) determined first on Rh, but found to be similar for more common Fischer-Tropsch catalysts (Ru, Fe, Co) showed that these are readily incorporated into the alkene and the alkane products. In addition, an increase in the rate of hydrocarbon formation was observed during vinylic but not ethyl addition. These data indicate that the participation of vinyl intermediates is an integral part of the surface polymerization mechanism, specifically, vinyl (alkenyl) intermediates couple with surface methylene in hydrocarbon formation ... 

The extent to which surface tension can be controlled by fluoroalkyl-containing coupling agent type treatments is summarized in Table 1. Its purpose is to simply illustrate the range of control possible detailed comparisons are unwarranted because of differences in sample preparation and choice of substrate, data acquisition and treatment. Some of the critical surface tensions (crc) are obtained with -alkanes, some with other liquids. Some of the dispersion force components (of) and polar components (of) of solid surface tension are derived by use of different equations. The reader is referred to the key references in Table 1 for full details. 

Catalytic membrane reactors are not yet commercial. In fact, this is not surprising. When catalysis is coupled with separation in one vessel, compared to separate pieces of equipment, degrees of freedom are lost. The MECR is in that respect more promising for the short term. Examples are the dehydrogenation of alkanes in order to shift the equilibrium and the methane steam reforming for hydrogen production (29,30). An enzyme-based example is the hydrolysis of fats described in the following. 

The reduction of aldehydes and ketones to alkanes. Condensation of the carbonyl compound with hydrazine forms the hydrazone, and treatment with base induces the reduction of the carbon coupled with oxidation of the hydrazine to gaseous nitrogen, to yield the corresponding alkane. 

Dialkynyl ketones.1 In the presence of Cl Pd[P(C6H5),]2 1 couples with al-kynyltin compounds (2) to give (N-phenyl)dialkynylimines (3) in 30-75% yield. These products are hydrolyzed to dialkynyl ketones (4) by aqueous acetone (BF, etherate) in —60% yield. Under the same conditions, Grignard reagents undergo coupling to alkanes. 

A new mixing rule has been proposed and tested coupled with SRK EOS and UNIFAC in this work. The new mixing rule, which is obtained by introducing a correction parameter to the Ge from the original UNIFAC in MHV1, is accurate for both binary and ternary gas/large n-alkane systems. The correction parameters have been correlated as a simple function of carbon number for a certain kind of gas/n-alkane system, which is convenient for engineering purposes. 

The complexes (l,5-cyclooctadiene)(2,4-pentanedionato)-palladium(II) and platinum(II) tetrafluoroborate are air-stable solids, soluble in polar organic solvents such as chloroform, methylene chloride, acetonitrile, acetone, or methanol but insoluble in nonpolar solvents such as alkanes, benzene, or ether. Their solutions in acetone have conductivities typical of 1 1 electrolytes. Their proton magnetic resonance spectra (in CDC13 solutions, internal tetramethylsilane reference at 60 MHz.) show peaks due to coordinated cyclooctadiene at 3.78 and 6.7-7.4r (Pd) and at 4.25 and 6.9-7.6r (Pt) and due to the chelated /3-diketone at 4.39 and 7.88r (Pd) and at 4.15 and 7.81r (Pt) with the expected area ratios. In the spectrum of the platinum compound coupling with the 95Pt isotope (33 %... 

Alkanes, RH (Sec. 7.7) (Sec. 10.7) (Sec. 10.8) (Sec. 19.9) from alkenes by catalytic hydrogenation from alkyl halides by protonolysis of Grignard reagents from alkyl halides by coupling with Gilman reagents from ketones and aldehydes by Wolff-Kishner reaction... 

Coupling with a diorganocopper reagent to yield an alkane (Sec. 10.8)... 

Lithium diorganocopper reagent (Gilman reagent), LiR2Cu Couples with alkyl halides to yield alkanes (Section 10.8). 

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