Amides butylated

To a vigorously stirred suspension of 2 mol of lithium amide in 2 1 of liquid atimonia (see II, Exp. 11) was added in 15 min 1 mol of propargyl alcohol (commercial product, distilled in a partial vacuum before use). Subsequently, 1 mol of butyl bromide was added dropwise in 75 min. After an additional 1.5 h, stirring was stopped and the ammonia was allovied to evaporate. To the solid residue were added 500 ml of ice-water. After the solid mass had dissolved, six extractions with diethyl ether were performed. The (unwashed) combined extracts were dried over magnesium sulfate and then concentrated in a water-pump vacuum. Distillation of the residue through a 40-cm Vigreux column afforded 2-heptyn-l-ol, b.p. 

Lithium amides of primary / fZ-alkylamines yield N-(/ f2 -alkyl)-0-(/ f2 -butyl)hydroxylamines, whereas lithium amides of primary alkylamines yield A/-alkylbenzamides and LiOO—due to nucleophilic attack on the carbonyl group (245). 

A/- -toluene su1fony1)-T-phenylalanine (62), L-histidine methyl ester (63), A/-acetyl L-valine /-butyl amide (64), etc, are used as chiral addends. 

The piedominant use of P-picoline (3) is as a starting material for agrochemicals and pharmaceuticals. For example, it is used to make insecticides such as chlorpyrifos (43), food additives such as niacin (27) and its amide (26), and herbicides such as fluazifop-butyl [69806-50-4] (63). 

Iminoboianes have been suggested as intermediates in the formation of compounds derived from the pyrolysis of azidoboranes (77). The intermediate is presumed to be a boryl-substituted nitrene, RR BN, which then rearranges to the amino iminoborane, neither of which has been isolated (78). Another approach to the synthesis of amino iminoboranes involves the dehydrohalogenation of mono- and bis(amino)halobotanes as shown in equation 21. Bulky alkah-metal amides, MNR, have been utilized successfully as the strong base,, in such a reaction scheme. Use of hthium-/i /f-butyl(ttimethylsilyl)amide yields an amine, DH, which is relatively volatile (76,79). 

The aminolysis of esters of pyrimidine occurs normally to yield amides. The reagent is commonly alcoholic ammonia or alcoholic amine, usually at room temperature for 20-24 hours, but occasionally under refiux aqueous amine or even undiluted amine are used sometimes. The process is exemplified in the conversion of methyl pyrimidine-5-carboxylate (193 R = Me) or its 4-isomer by methanolic ammonia at 25 °C into the amide (196) or pyrimidine-4-carboxamide, respectively (60MI21300), and in the butylaminolysis of butyl ttracil-6-carboxylate (butyl orotate) by ethanolic butylamine to give A-butyluracil-5-carboxamide (187) (60JOC1950). Hydrazides are made similarly from esters with ethanolic hydrazine hydrate. 

In some cases acid amide formation was observed on attempted deprotonation at oxaziridine ring carbon. 2-r-Butyl-3-(4 -nitrophenyl)oxaziridine (67) was converted to the anion of acid amide (68) by sodium amide (69TL3887), while 2-(4 -nitrobenzoyl)-3-phenyl-oxaziridine (69) afforded the diacylimide (70) by addition of cyclohexylamine to its benzene solution at room temperature (67CB2593). 

Me3SiI, CH2CI2, 25°, 15 min, 85-95% yield.Under these cleavage conditions i,3-dithiolanes, alkyl and trimethylsilyl enol ethers, and enol acetates are stable. 1,3-Dioxolanes give complex mixtures. Alcohols, epoxides, trityl, r-butyl, and benzyl ethers and esters are reactive. Most other ethers and esters, amines, amides, ketones, olefins, acetylenes, and halides are expected to be stable. 

Equations 4-8 illustrate some mild methods that can be used to cleave amides. Equations 4 and 5 indicate the conditions that were used by Woodward and Eschenmoser, respectively, in their synthesis of vitamin B,2- Butyl nitrite," nitrosyl chloride, and nitrosoniurn tetrafluoroborate... 

Amides 1-4 all adopt conformations in wiiich a i-butyl group has an axial-like position and, as a result, a non-chair conformation of the six-membered ring. Comment on the origin of this stmctural effect. 

The carboxamidomethyl ester was prepared for use in peptide synthesis. It is formed from the cesium salt of an A-protected amino acid and o -chloroacet-amide (60-85% yield). It is cleaved with 0.5 M NaOH or NaHC03 in DMF/H2O. It is stable to the conditions required to remove BOC, Cbz, Fmoc, and t-butyl esters. It cannot be selectively cleaved in the presence of a benzyl ester of aspartic acid. ... 

Equations 1-10 illustrate some mild methods that can be used to cleave amides. Equations 1 and 2 indicate the conditions that were used by Woodward and Eschenmoser, respectively, in their synthesis of vitamin B12. Butyl nitrite, nitrosyl chloride, and nitrosonium tetrafluoroborate (NO BF4 ) have also been used to cleave amides. Since only tertiary amides are cleaved by potassium -butoxide (eq. 3), this method can be used to effect selective cleavage of tertiary amides in the presence of primary or secondary amides.(Esters, however, are cleaved by similar conditions.) Photolytic cleavage of nitro amides (eq. 4) is discussed in a review. 

Cyclization of amide 312 by treatment with TFA gave 1 li-butyl-1,3, 4,6,7,1 l -hexahydro[l,4]oxazino[3,4-a]isoquinolin-4-one 313 (97JOC2080). 

As shovm above, the attachment of the aromatic ring to the carbon chain bearing the basic nitrogen may be accomplished through an ester or an amide configured in either direction. A simple ether linkage fulfills this function in yet another compound that exhibits local anesthetic activity. Thus, alkylation of the mono potassium salt of hydroquinone with butyl bromide affords the ether (77) alkylation of this with w-C3-chloropropyl)morpholine affords pramoxine (78)... 

I he diaryImethanes (105). The protons on the methylene group of lliese compounds are sufficiently acidic to be removed by strong b.ises such as sodium amide or butyl lithium. Alkylation of the resulting carbanion with w-C2-chloroethyl)dimethylamine affords,... 

Photolytic Reaction in Sunlight A mixture of olefin (0.01 mole), formamide (40 g), r-butyl alcohol (20 ml), and acetone (5 ml) is placed in a Pyrex Erlenmeyer flask, which is then flushed with nitrogen, stoppered, and situated in direct sunlight for 1 day. A solution of olefin (0.04 mole), /-butyl alcohol (25 ml), and acetone (5 ml) is then added in four equal portions at 1-day intervals, and finally, the flask is left in sunlight for an additional 2 days. Work-up of the solutions as in the above procedure gives the desired amide in comparable yields. 

Chemical Name N-carboxy-/3-alanyl-L-tryptophyl-L-methionyl-L-aspartylphenyl-L-alanin-amide N-tert-butyl ester... 

N-tert-butyl-2-(5-benzyloxy-6-hydroxymethyl-2-pyridyl )-2-hydroxyacet amide... 

Other recent works in this field, studies on the transport of alkali and alkaline earth cations with p-zerr-butyl calix[n]arene esters and amides, were carried out by Arnaud-Neu et al. [20] and Casnati et al. [21]. They prepared 1,3-alternate calix[4]arene-crown-6 as a new class of cesium selective ionophore. 

Amino groups are often protected as their tert-butoxycarbonvl amide, or Boc, derivatives. The Boc protecting group is introduced by reaction of the amino acid with di-fert-butyl dicarbonate in a nucleophilic acyl substitution reaction and is removed by brief treatment with a strong organic acid such as trifluoro-acetic acid, CF3C02H. 

Butylation of ethyl phenylacetate, /-butyl phenylacetate, and ethyl 2-phenylhexanoate has also been accomplished with M-butyl bromide and sodium hydride in refluxing monoglyme in 64%, 66%, and 56% yields, respectively.6 In contrast to the sodium amide reactions above, however, careful fractionation of the crude products was required to obtain pure products. 

Besides the technical method starting from naphthalene, phthalic acid and its substituted derivatives can be prepared by oxidation of o-xylene to phthalic acid with potassium permanganate. This compound can be subsequently transformed via an anhydride, imide, and amide to a derivative of phthalonitrile, which is the more convenient starting material for several coordination compounds. The synthesis of the ferf-butyl-substituted dicarbonitrile, which is a very common starting material for highly soluble phthalocyanines, is shown below.97,105... 

In spite of their intrinsic synthetic potential, addition reactions of metal enolates of non-stabilized esters, amides, and ketones to epoxides are not widely used in the synthesis of complex molecules. Following the seminal work of Danishefsky [64], who introduced the use of Et2AlCl as an efficient catalyst for the reaction, Taylor obtained valuable spiro lactones through the addition reaction of the lithium eno-late of tert-butyl acetate to spiro-epoxides, upon treatment of the corresponding y-... 

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