Fert-butylamine

Dibromo-l,3-dimethylcyclopropanoic acid See 2,2-Dibromo-l,3-dimethylcyclopropanoic acid fert-Butylamine See other ORGANIC bases... 

This preparation illustrates a general method for the synthesis of N-methylalkylamines. The submitters have used it to prepare N-methylbutylamine (Note 4) and N-methylallylamine, and the checkers have used it to prepare N-methylisopropylamine (80%), N-methylisobutylamine (67%), N-methyl-fert-butylamine (52%), and N-methyl-2-methoxyethylamine (55%). Secondary amines are useful as starting materials for the synthesis of 1,1-disubsti-tuted hydrazines and asymmetric amine imides. 

The nitrolysis of tertiary amines in the form of fert-butylamines and methylenediamines has been used to synthesize numerous polynitramine-based energetic materials. In these reactions one of the N-C bonds is cleaved to generate a secondary nitramine and an alcohol the latter is usually 0-nitrated or oxidized under the reaction conditions (Equation 5.15). The ease in which nitrolysis occurs is related to the stability of the expelled alkyl cation. Consequently, the fert-butyl group and the iminium cation from methylenediamines are excellent leaving groups. 

In a closely related example, a Mannich reaction of the somewhat more complex phenol (20-1) with formaldehyde and fert-butylamine gives the aminomethylated product (20-2). Hydrolysis of the acetamide protecting group then affords the corresponding aniline (20-3). Alkylation with the quinoline (17-6) in this case also proceeds on aniline nitrogen. The selectivity over the more basic secondary side nitrogen can probably be ascribed to steric hindrance about the latter. There is thus obtained tebuquine (20-4) [22]. 

See Potassium permanganate Acetone, fert-Butylamine See other NITROALKANES... 

The mass spectrum of fert-butylamine follows. Use a diagram to show the cleavage that accounts for the base peak. Suggest why no molecular ion is visible in this spectrum. 

Table 1 Principal Mass Peaks of N/N-di-n-Butyl-fert-butylamine and Tri-n-Butylamine...

Modifications are made also in order to use this reaction to conjugate nucleosides to erythrocyte surfaces, allowing use of the coated cells as targets for assays of antibody-forming splenic lymphocytes. Nucleoside, 10-20 mg, is oxidized in 1.5 ml of 0.1 M sodium periodate in 0.15M NaHCOa for 20 min at room temperature the reaction is stopped by the addition of 15 /zl of ethylene glycol. Sheep erythrocytes are washed twice with 0.15 M NaHCOs, and 0.5 ml of packed cells is then suspended in 2.0 ml of the bicarbonate solution in a40-ml centrifuge tube. The oxidized nucleoside is added dropwise to the cell suspension and the mixture is kept at room temperature for 15 min. fert-Butylamine borane (Aldrich Chemical Co.), 100 mg in 5 ml of 0.15 M NaHCOs, is added. The suspension is kept at room temperature for 3 min, and the tube is then quickly filled with bicarbonate solution and centrifuged at 1500 rpm for 10 min. 

Reduction with lithium aluminum hydride allows a differentiation from the isomeric nitrones.8 Whereas 2-ter<-butyl-3-phenyloxazirane (9) gives benzylidene-fert-butylamine [Eq. (10)], reduction of the isomeric nitrone leads to iV-benzyl-iV-tert-butylhydroxylamine [Eq. 

Monosubstituted chloramines have not received much attention. The reaction of A-chloro-fert-butylamine with di( < r -butyl)magncsium gives di(fert-butyl) amine in 10% yield.67 Butylmagnesium chloride and /V-chloromcthylaminc produce mostly methylamine by reduction and only 14% of A-methylbutylamine 68... 

Intramolecular displacement of benzylic chlorides by nitrile anions was previously demonstrated as an efficient method making substituted pyrrolidines " however, the question of enanti-oselectivity was not addressed. Recent works on the synthesis of substituted cyclopentane showed that intramolecular enolate displacement of benzylic phosphate proceeded in clean inversion. Thus, it was envisioned that an appropriately substituted cyano phosphonate could be used to construct the pyrrolidine ring (Scheme 5.23). This intermediate could potentially be produced by the addition of a fert-butylamine to acrylonitrile. The desired amine could be produced via reaction... 

In order to obtain evidence for or against these ideas we have begun an intensive study of the reactions of ozone with a variety of amines. This paper summarizes results from the ozonation of fert-butylamine and of tri-n-butylamine, which furnish evidence for the competitions indicated by Reactions 2, 3, and 4. Additional details will be published elsewhere. 

In a typical run, 5 mmoles of fert-butylamine in chloroform reacted with 4.1 mmoles of ozone in an ozone-nitrogen stream at about —60°C. to give 0.9 mmole (18%) of 2-methyl-2-nitropropane (XI), 0.9 mmole (18% ) of tert-h iiy isocyanate (XVI), and 3.0 mmoles (60% ) of tert-butylammonium chloride (XIV). In a separate but similar run, 3.5 mmoles of molecular oxygen were determined as a product. Under the conditions of the reaction no significant reaction occurred between ferf-butylamine and chloroform in the absence of ozone or between ozone and chloroform in the absence of the amine. 

Synthesis of j8,y-Unsaturated Amines. 1,1-Disubstituted alkenes can be converted into the corresponding 8, /-unsaturated amines, valuable synthons in medicinal chemistry, and versatile synthetic intermediates, via a three-step protocol with moderate to good yields. The initial formation of a, 8-unsaturated diphenyl-sulfonium triflates from alkenes, such as a-methylstyrene, and the combination of diphenyl sulfoxide and TfzO, is followed by double bond migration to form /3,y-unsaturated sulfonium triflates. Subsequent nucleophilic substitution with primary or secondary amines such as fert-butylamine leads to the corresponding p,y-unsaturated amines (eq 10). ... 

Sterically unhindered amines such as pyrrolidine, piperidine, n-butylamine, and neo-pentylamine, etc., all react faster than Py, and the reaction exhibits second-order kinetics, indicating that the rate-determining step involves the direct reaction between the dimer and the amine. Sterically more-hindered amines, such as fert-butylamine, di-n-butylamine, and quinuclidine, exhibit first-order... 

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