Tributyl amine

Tributyl amine, palladium acetate, triphenyl phosphine from Fluka AG and N,N-dimethylformamide and formic acid from Farmitalia Carlo Erba Chemicals were used without further purification. 

When cyclohexene is used as substrate, cyclohexene oxide is formed with selectivities exceeding 95% at conversions up to 89% [89]. The activity increases with increasing Mo content and is poisoned by tributyl amine, but not by triphenylamine, which is too bulky to enter the zeolite pores. These results... 

The earlier work on chloroacetone (18,19) already indicated that trialkyl amines were superior to other bases for this reaction. Therefore the decision to use trialkyl amines to scavenge HCl was already determined by the literature precedent. However, when compared to the tributyl amine, smaller amines might be preferred since they could boost the reactor productivity by reducing the volume. Unfortunately, for unknown reasons, the process did not work as well with the simpler amines. Both tripropyl amine and triethyl amine displayed both lower rates and lower selectivity for methyl pivaloyl acetate. (See Table 6.)... 

To a 300 mL Hastelloy-B autoclave was added 110 mL (87.0 g, 2.71 mol) of methanol, 30.0 mL (23.3 g, 126 mmol) of tributyl amine, 11.0 mL (11.3 g, 83.8 mmol) of 1-chloropinacolone, and 0.1 mmol of catalyst. The autoclave was sealed, flushed with carbon monoxide, and pressurized to 30 psi with CO. The autoclave was then heated to 105°C and the pressure was adjusted to 80 psi. The temperature and pressure were maintained using a continuous carbon monoxide feed for 3 h. The mixture was then cooled and analyzed by gas chromatography. Phosphine effects and additional comparison were conducted at 150 psi of CO as noted in the tables. 

Ballard and Bamford (43) also investigated the kinetics of the polymerisation of D,L-phenyl alanine NCA initiated by tributyl amine in nitrobenzene. This reaction does not ensue1 in pure tertiary amine (11), but it proceeds rapidly in polar solvents. (For a tentative explanation of this observation see p. 49.) However, the polarity does not appear to be a necessary condition for a rapid reaction since a fast polymerisation initiated by triethyl amine in benzene was observed by Blout (49). It seems, therefore, that the role of solvent in these reactions needs further and extensive examination (see also p. 48). In the tributylamine-initiated polymerisation, sarcosine NCA again proved to be inert (44) under conditions which led to a rapid polymerisation of the non-N-substituted NCA s. 

The time conversion curves of the polymerisation initiated by tributyl amine are shown in Fig 11. They resemble the curves presented in Fig. 10, indicating the basic similarity of the process initiated by tertiary amines, by salts of carboxylic adds and by LiCl in dimethyl... 

Ether solutions based on TAA salts are not reduced on noble metal electrodes. The major cathodic reaction of these solutions involves the cation reduction to trialkyl amine, alkane, and alkene (which are the stable disproportion products of the alkyl radical formed by the electron transfer to the cation) [3], Electrolysis of ethers such as THF or DME containing TBAP, formed in the catholyte tributyl amine, butane and butene, were unambiguously identified by NMR and GCMS analysis [3], In the presence of water (several hundred ppm and more), the electrolysis products were found to be tributyl amine and butene (butane was not detected) [3], The potential of this reduction reaction is higher than that of the dry solution, and it is clear that the initial electroactive species in this case is the... 

The dynamics of reversible onium ion formation has been studied by generating carbenium ions in the presence of nucleophiles using pulse radiolysis or flash photolysis, and following the rate of disappearance of the carbenium ions by UV. As discussed in Chapter 2, the kinetics of reaction of various electrophiles with nucleophiles obey a general reactiv-ity/selectivity relationship. The rates of reaction of various nucleophiles with carbenium ions are summarized in Table 9. These rates often approach diffusion controlled limits (k 10 ° mol-,-L-sec l). The rates are slower for less nucleophilic and less electrophilic compounds, and are particularly slow with sterically hindered amines such as lutidine (2,6-dimethylpyridine) [63]. Solvent effects are minimal when the reactions are diffusion controlled, although tributyl amines react slower with carbenium ions in more nucleophilic dichloroethane than in methylene chloride. 

Another 20 /o w/v emulsion, trade-name Perftoran, based on an FDC and F-[l-(4-methylcyclohexyl)piper-idine] (FMCP, 8) mixture emulsified with a poloxamer was developed in Russia (Russian Academy of Sciences/ Perftoran Company, Pushshino, Russia). " Perftoran is filter-sterilized and stable for about 1 month at 4-8°C but requires freezing for longer storage. The Russian health authorities licensed it in 1997 for a wide range of indications. A highly stable 20 /o w/v F-tributyl-amine/Pluronic F-68 emulsion, Fluosol-43 (later renamed Oxypherol), was commercially available for many years for experimental use. 

The gel compositions (in molar ratios) were as follows, using a mixture of TBA (tributyl-amine Huka) and DPTA (dipentylamine 99%, Janssen) as organic bases, and LUDOX AS-40 (Du Pont) or TEOS (tetraethylorthosilicate 98%, Janssen) as silicon sources ... 

Cyclooctene, 2,3-dihydrofuran, tributyl amine, bicyclooctyl, and other products... 

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