Tertiary butyl amine

Opening of the oxirane with tertiary butyl amine would then complete construction of the 3-blocking side chain (40). Displacement of chlorine by hydrazine then affords... 

A special application of LLC is ion pair partition chromatography. In this procedure, the ionic form of the solute (analyte) is paired with an appropriate counter ion of decreased polarity, e.g. tetra-tertiary-butyl amine. This ion pair is then partitioned between selected mobile and stationary phases to achieve the desired separation. In practice, ion pair chromatography is commonly conducted by utilizing a mobile phase comprised of a miscible aqueous/organic mixture containing a relatively high concentration of counter ion. The technique is applicable to analysis of many types of ionic compounds (10). 

Application The Snamprogetti Cracking Technology allows producing high-purity isobutylene, which can be used as monomer for elastomers (polyisobutylene, butyl rubber) and/or as an intermediate for the production of chemicals—MMA, tertiary-butyl phenols, tertiary-butyl amines, etc. 

Tertiary butyl amine is derived from reacting ammonia with isobutene with a catalyst such as ammonium iodide and chromium chloride as shown in Figure 10.14. 

Primary alkyl amines RNHi can be convertedto alkyl halides by (1) conversion to RNTs2 (p. 447) and treatment of this with I or Br in DMF, or to N(Ts)—NH2 derivatives followed by treatment with NBS under photolysis conditions, (2) diazotization with terr-butyl nitrite and a metal halide such as TiCU in DMF, or (3) the Katritzky pyrylium-pyridinium method (pp. 447,489). Alkyl groups can be cleaved from secondary and tertiary aromatic amines by concentrated HBr in a reaction similar to 10-71, for example,... 

The reaction of tertiary aromatic amines with butyl nitrite has been investigated in detail. The main products arise from 7V-dealkylation/7V-nitrosation, e.g. equation 91270. 

As indicated above, tertiary aromatic amines are directly C-nitrosated. The usual reagents are sodium nitrite and dilute hydrochloric acid, sodium nitrite and glacial acetic acid containing concentrated hydrochloric acid, and nitrite esters with hydrochloric acid [21a, 27]. While tertiary amines with such complex alkyl groups as found in A,A-di(3,5,5-trimethylhexyl)aniline are readily nitrosated [25], of the four A-butyl-A-methylaniline isomers, JV-r-butyl-A-methylaniline does not undergo the reaction, and even the nitroso compounds which did form were only unstable oils [27]. 

Ketone-derived chiral /V-acylhydrazones may also be prepared by direct condensation with /V-aminooxazolidinone 2a (Table 2) [45, 49]. Mixtures of E/Z isomers were usually obtained, although ketone /V-acylhydrazones 9d and lOd, with highly branched tertiary butyl (7-Bu) substituents, were formed as single isomers. Pyruvate-derived hydrazone (E)-11 was formed with high selectivity, and the major isomer was readily separated from its minor (Z)-isomer by flash chromatography [45], Others have recently used these amination and condensation... 

The slight effect of solvent upon the rate of decomposition is characteristic of tertiary dialkyl peroxides. For example, the rate of decomposition of di-r-butyl peroxide is altered only slightly by changing from the gas phase through hydrocarbon solvents to tri-n-butyl amine (Table 66). These results indicate that there is little ionic character in the activated complex of the rate-determining step (2). 

The authors studied the polymerization of formaldehyde with amines including tertiary amines at —78°C in various solvents (Table 1), and determined the conversion after 15 min reaction time. Tertiary amines are highly reactive initiators for formaldehyde polymerizations even at the level of 10 mole T per mole 1 of formaldehyde. The reactivity of the amine is related to its pXg value but also to the branching of the aliphatic side chains of the substituents on the nitrogen atom. Branched amines, especially when the branching is on the a-carbon atom as in the case of a tertiary butyl group, are less effective initiators than tertiary amines with n-alkyl chains. The pX a of the amine is not the essential feature for an efficient tertiary amine initiator, because pyridine was almost as effective as tri-n-butylamine but quinoline, with a similar pK g as pyridine, is almost inactive (Table 1). 

Double bonds between carbon and nitrogen in secondary and tertiary cyclic amines are formed on treatment with mercuric acetate [401, 402, 1091], silver oxide [375], or tert-butyl hypochlorite [707]. tert-Butyl hypochlorite converts methyl pyrrolidine-2-carboxylate into methyl 1-pyrrol ine-2-carboxylate in 71% yield [707], and mercuric acetate transforms 2-terr-butylpiperidine into 2-tm-butyl-l-piperideine in 75% yield [1091]. Tertiary cyclic amines are dehydrogenated by mercuric acetate via quaternary salts [401,402]. l-Methyl-2-ethylpiperidine yields ultimately 1-methyl-2-ethyl-2-piperideine [402] and quinolizidine A -dehydroquin-olizidine [401] (equation 34). 

Selectivity may also be achieved by having a very bulky radical that is unable to abstract certain protons. A similar point is observed with the use of sterically hindered bases to remove only primary hydrogens instead of the most acidic ones in the molecule. An example of a sterically hindered radical is that formed from A-chloro-di-/-butyl amine, which abstracts primary hydrogens 1.7 times faster than tertiary ones. 

We chose 2-chlorotrityl chloride resin for the attachment of acrylic acid, because in solution-phase chemistry the best results have been obtained by using aryl acrylates or (erf-butyl acrylates [21], In addition to DABCO (1,4-diazabicyclo [2.2.2]octane) - the most common tertiary cyclic amine for this type of reaction - we also used the more reactive 3-quinuclidinol (3-hydroxy-quinuclidine, 3-HQN) for the Baylis-Hillman reaction with aldehydes. We used 26 different aldehydes and obtained good to excellent purities, as determined by analytical HPLC. 

In other studies the influence of N substitution on the effectivity of 4-benzoyloxy-2,2,6,6-tetramethylpiperidine was studied [116-118]. In this case the effectivity decreased in the order O > O-butyl > butyl > hydrogen > acetyl. It was shown that the tertiary hindered amines were oxidized and converted to the parent secondary amine. 

Macroporous glycidyl methacrylate-ethylene glycol dimethacrylate (GMA-EGDM) copolymer beads were synthesised and characterised for pore volume and surface area. These reactive copolymers were derivatised with 2-picolyl amine and coordinated with chromium and vanadium ions. The peroxocomplexes of these supported metal complexes were generated by the addition of hydrogen peroxide / tertiary butyl hydroperoxide(tert. -BHP) and shown to catalyse a variety of oxidation reactions. 

Methylenation. 2-(Phenylthio)ethanols (2), prepared from ketones (1) and phenylthiomethylhthium, undergo reductive /3-ehmination to give 1-alkenes when treated with the black reagent prepared from TiCU and L1A1H4 in the presence of a tertiary amine [ 1,8-bis(dimethylamino)naphthalene or tri-n-butyl-amine]. Benzene-dioxane is used as solvent for the elimination (4 hr. reflux). ... 

Photoelectron Spectroscopy.—The spectra of the reactive methylidynephosphines (70 R = Ph, TMS) have been compared with the stable tertiary butyl compound. " The vertical ionization potentials of trimethyl-, methylphenyl-, and triphenyl-phosphines have been measured. The basicity order in the gas phase is the reverse of that in solution and of the basicity order of amines in the gas phase. " ... 

The reactions of tertiary halides are frequently different from those of the corresponding primary compounds. The former are readily converted into unsaturated hydrocarbons as the result of the elimination of hydrogen halide. Thus, tertiary butyl iodide when heated with ammonia does not form an amine as normal butyl iodide does, but is converted into isobutylene. The effect of the positive or negative nature of the group in combination with a halogen atom on its reactivity when brought into contact with other compounds, will be considered in the discussion of acyl halides (272, 275). 

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