Trimethylamine complexes

Bitumen Ionomers. Moisture-resistant asphalts (qv) have been prepared by reaction of metal oxides with acid-functionalized bitumens (75). Maleic anhydride or sulfur trioxide/trimethylamine complexes have been used successfully for introduction of acid groups into asphaltic bitumens. 

Fig. 2. Components of Li enthalpies of complexation with methylamines. Successive steps indicate the effect on energy of interaction between Li and the amine of inclusion of additional components of the binding energy. The diagram shows that the permanent dipoles on amines (the charge on the nitrogen of the isolated amine) favor ammonia over trimethylamine complexation, but that polarizability and inductive effects (shift of negative charge onto the nitrogen in the complex) cause a massive turnaround in favor of complexation with trimethylamine rather than ammonia. Of particular importance is the near inversion of order caused by the addition of repulsive van der Waals terms. Modified after Ref. (9).

A sample of the vacuum distilled pyridine complex exploded in a heated capillary sampling tube [1]. Detonation of the trimethylamine complex [2], at or near 200°C [3] is also noted. 

The residue from sublimation of the complex with dioxane is explosive, and the complex should not be dried by heating. The trimethylamine complex may also... 

The aluminium hydride-trimethylamine complex releases hydrogen by reaction with carbazole giving the complex 80. ° ... 

Borane trimethylamine complex [75-22-9] M 73.0, m 94-94.5 , b 171 /atm. Sublimed using equipment described in JACS 59 780 1937. Its vapour pressure is 86mm at 100 . Colourless hexagonal crystals varying from needles to short lumps, slightly soluble in H2O (1.48% at 30°), EtOH (1%), hexane (0.74%) but very soluble in Et2O, and AcOH. Stable at 125 . [JACS 59 780 1939,104 325 1942]. 

The residue from sublimation of the complex with dioxane is explosive, and the complex should not be dried by heating. The trimethylamine complex may also explode on sublimation [1]. Triethynylaluminium or its complex with diethyl ether may decompose explosively on heating. Sublimation is not therefore advised as a purification method [2]. See other METAL ACETYLIDES... 

Reaction of sodium naphthalide with B2C14 at room temperature was reported to give a liquid product with a suggested structure, 17. The compound 17 reacts with four equivalents of (CH3)3N to form an adduct which decomposes above 100 °C to give the bis(trimethylamine) adduct of B2C14 and an unstable product that is thought to be 18 (Scheme 3). It was reported that the trimethylamine complex of tetra(methyl)diborane(4) was obtained from the reduction of bromodimethylborane with sodium or silver in trimethylamine.52... 

The qualitative features of the spectra are in conformity with the observations made on the ether. HF or ether. HC1 systems. Millen and Zabicky24 examined the complexes of methanol with trimethylamine, dimethylamine, methylamine, ammonia and aziridine. In all cases methanol is the proton donor and the nitrogen lone pair is the electron acceptor. In the methanol trimethylamine-complex spectrum the central band is at 3355 cm-1. One subband is resolved at each side, at about 3495 and 3200 cm-1. Using a large excess of amine the absorbance of the bands is proportional to the product of the pressures of the two components so the spectrum must be attributed to the 1 1 complex. From the spacing a value of 145 cm-1 can be infered for v . 

Tris(trifluorovinyl)aluminium may be obtained as the trimethylamine complex, as indicated in Figure 10.33. 

It is reported that the trimethylamine complex of tetramethyldiborane(4) was obtained from the reduction of bromodimethylborane with sodium or silver in trimethylamine (92). 

As described above, the bis(trimethylamine) complex of tetramethyl-diborane(4) may be rather more stable than the parent compound. 

The trimethylamine complex is stable to water, methanol, and hydrogen chloride at room temperature. Heating with HCl in a sealed tube leads to the uptake of two molecules of the hydrogen halide, suggesting formation of an ionic product (53). 

Sulfonic acids. Complexes of sulfur trioxide have been used to introduce the SO3H group to organic molecules. For example, organolithium reagents are converted to sulfonic acids by the trimethylamine complex and the dioxane complex is useful for replacing a silyl... 

The methyne proton of tris(pyrazolyl)methane is sufficiently acidic to be removed by raBuLi, and the resulting reactive intermediate readily reacts with electrophiles. Klaui prepared two new anionic tripodal nitrogen water-soluble ligands (the lithium salts of tris(pyrazolyl)- and tris(3-tert-butylpyrazol)-methanesulfonic, Tpms and Tmps B" respectively) by addition of lithiated tris(pyr-azolyl)methane to a sulfur trioxide-trimethylamine complex (Scheme 25).146... 

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