Tert- Alkyl ferf-butyl

When writing an alkane name, the nonhyphenated prefix iso- is considered part of the alkyl-group name for alphabetizing purposes, but the hyphenated and italicized prefixes sec- and tert- are not. Thus, isopropyl and isobutyl are listed alphabetically under i, but sec-butyl and ferf-butyl are listed under b. 

Three peroxides with aromatic substituents have reported enthalpy of vaporization data, all from the same source". The enthalpies of vaporization of cumyl hydroperoxide and ferf-butyl cumyl peroxide are the same, which makes us skeptical of at least one of these values. The calculated b value for cumyl hydroperoxide is 31.5, consistent with the alkyl hydroperoxides. The calculated b value for tert-butyl cumyl peroxide is 15.4 and more than twice that for the mean of the dialkyl peroxides. The structurally related tert-butyl p-isopropylcumyl peroxide has a b value of 8.8 and so is consistent with the other disubstituted peroxides. 

Carbazole can be efficiently tetra-ferf-butylated with tcrt-butylchloride and aluminium chloride at room temperature giving 141 K. 4i,85. traces of 3,6-di- and 1,3,6-tri-tert-butylcarbazoles are also produced. 3-Formyl-2-hydroxycarbazole is alkylated at C-1 with dimethylallyl chloride in the presence of 30% aqueous potassium hydroxide. ... 

The slightly unexpected behaviour of the dioxolanes 9, i.e., alkylation of the enolate on the face syn to the substituents has also been observed with the tert-butyl thioester of (2R,4,V)-2-ferf-butyl-1,3-dioxolane-4-carboxylic acid (16)76-78. Treatment of 16 with 1 equivalent of LDA in tetrahy-drofuran. in the presence of HMPA and RX at —78 °C preferentially furnished the isomer 17. 

The anti selectivity increases as the disubstituted side of the double bond becomes more crowded (Scheme 8). This is illustrated with the trisubstituted alkenes 16, 17 and 1351. Alkene 16 shows the normal cis effect selectivity where only 10% of the anti ene adduct is formed. However, as the size of the cis alkyl substituent increases from methyl in 16, to isopropyl in 17 and ferf-butyl in 13, the anti selectivity increases from 10% to 42% and to >97%, respectively. The same trend is also noted in substrate 19. A substantial deviation from cis effect selectivity is observed by replacing one methyl group in 18 with a tert-butyl group in 19. The totally unreactive methylene hydrogens in 18 (cis effect) become reactive in 19, producing the exo ene adduct in 38% yield. 

Alkoxyalkyl Alkyl Peroxides. ferf-Butyl tetrahydropyran-2-yl peroxide (1, where R3 = tert - butyl. H = OR4, R1 = H, R2 and R4 = 1,4 -butanediyl, has been isolated. This is one of many examples of alkoxyalkyl alkyl peroxides which may be prepared by reaction of hydroperoxides with vinyl ethers. 

As is apparent in the last step, isobutane is not alkylated but transfers a hydride to the Cg+ carbocation before being used up in the middle step as the electrophilic reagent (tert-butyl cation 4). The direct alkylation of isobutane by an incipient tert-butyl cation would yield 2,2,3,3-tetramethylbutane,142 which indeed was observed in small amounts in the reaction of ferf-butyl cation with isobutane under stable ion conditions at low temperatures (vide infra). 

Many functional groups are stable under conditions for the alkylation of pseudoephedrine glycinamide enolates, including aryl benzenesulfonate esters (eq 18), rert-butyl carbamate and rerf-butyl carbonate groups (eq 19), tert-butyldimethylsilyl ethers, benzyl ethers, ferf-butyl ethers, methoxymethyl ethers, and alkyl chlorides. The stereochemistry of the alkylation reactions of pseudoephedrine glycinamide and pseudoephedrine sarcosinamide is the same as that observed in alkylations of simple A(-acyl derivatives of pseudoephedrine. 

The effects of various parameters on the ferf-butylation of phenol on the ZeoUte-H-beta have been studied". Alkylation of phenol in the vapor phase using Zeolite SAP-11 and ferf-butyl alcohol gives the ortho- and para-ferf-butylphenols, together with the 2, 6-di-ferf-butylphenol (equation 22). Vapor-phase alkylation of phenol with tert-butyl alcohol over solid superacid catalysts, such as sulfated zirconia" and mesoporous H-AMCM-41, gives para-fert-butylphenol as a major product in high regioselectivity. 

Tris[3-tert-butyl-4-(hydroxybenzyl)]mesitylene (III) was synthesized starting from 2-fert-butyl-6-chlorophenol, which in turn was prepared by the method of Kolka et al. (10). The 2-ferf-Butyl-6-chlorophe-nol was alkylated with a1,a3,a5-(trihydroxyhexamethyl)benzene (Aldrich) with the use of boron trifluoride etherate catalyst (II). A mixture of I and II was obtained, separated by fractional crystallization from methyl-cyclohexane. The structures of the two products were assigned on the... 

The prefix tert is found in ferf-butyl and ferf-pentyl because each of these substituent names describes only one alkyl group. The name ferf-hexyl cannot be used because it describes two different alkyl groups. (In older literature, you might find amyl used instead of pentyl to designate a five-carbon alkyl group.)... 

SAMPLE SOLUTION (a) The molecule has a terf-butyl group bonded to a nine-membered cycloalkane. It is tert-butylcyclononane. Alternatively, the ferf-butyl group could be named systematically as a 1,1-dimethylethyl group, and the compound would then be named (1,1-dimethylethyl)cyclononane. (Parentheses are used when necessary to avoid ambiguity, in this case the parentheses alert the reader that the locants 1,1 refer to substituents on the alkyl group and not to ring positions.)... 

Tert. alkyl esters. Barium ferf-butyl phosphite stirred and treated with bromine in water in the presence of Ba-hydroxide and Ba-carbonate at pH 8-9 at 20°, and the product isolated after 18hrs. barium ferf-butyl phosphate. Y 78%. F. e. s. E. Cherbuliez et al., Helv. 47, 1659 (1964). 

As an example, ferf-butyl (45)-l-methyl-2-oxoimidazolidine-4-carboxylate was used by Nunami and colleagues as a chiral auxiliary for DKR of a-bromo-carboxylic acids. In this case, the nucleophile was a malonic ester enolate and the role of the polarity of the solvent (hexamethylphosphoramide, HMPA) was demonstrated (Scheme 1.2). The alkylated products were further easily converted to chiral a-alkylsuccinic acid derivatives and chiral jS-amino acid derivatives. Moreover, these authors showed that this methodology could be extended to other nucleophiles such as amines." Therefore, the reaction of a diastereomeric mixture of tert-bvAy (45)-l-methyl-2-oxoimidazolidine-4-carb-oxylate with potassium phthalimide predominantly afforded fcrf-butyl (45)-1-methyl-3-((25)-2-(phthaloylamino)propionyl)-2-oxoimidazolidine-4-carboxylate in 90% yield and 94% diastereomeric excess (de). The successive removal of the chiral auxiliary afforded A-phthaloyl-L-alanine. 

Alkyl Group. Tertiary alkyl halides may be used in solvolyses with confidence that the reactions are proceeding by the Sj jl mechanism. Two compounds that allow you to examine the possible effects of the structure of the alkyl group on reaction rates are 2-chloro-2-methylpropane (ferf-butyl chloride) and 2[Pg.484]

The 3-(ferf-butyl)-4-hydroxyphenyl motif can likewise be incorporated in extended polyol assemblies. For example, Hostanox 03 ethane-1,2-diyl-bis(3,3-bis(3-(tert-butyl)-4-hydroxyphenyl)butanoate), a product of Clariant, is preferentially used as an antioxidant for plastics with high resistance against hydrolysis. It can be produced on a large scale by the reaction of p-tert-h xXy phenol with methyl acetoacetate in the presence of an alkyl mercaptan and final transesterification with ethylene glycol catalyzed by Bu2SnO (Scheme 2.72) [42]. 

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