F-butyl amine

The inlet tube is then replaced by a 300-ml. dropping funnel containing 202 g. (2 mols) of triethylamine. The triethylamine is added dropwise to the reaction mixture. During the addition, the reaction mixture is stirred and cooled by ice or cold water. After addition of the triethylamine, 73 g. (1 mol) of f-butyl-amine is added through the dropping funnel over a period of one hour. The slurry is stirred for 2 hours at room temperature and then finally heated to reflux for a period of 40 hours. 

A number of investigators have examined the ease of isomerization about the formal carbon-carbon bond in imine anions. " Bergbreiter and Newcomb determined an energy barrier of approximately 17 kcal mol" for rotation about this bond in both the lithium imine anions derived from cyclohexyl- and f-butyl-amine addition to acetaldehyde. The barrier for rotation for the corresponding anion derived... 

MBTS reacts with f-butyl amine to give TBBS and with cyclohexyl amine to give CBS, both of which are extremely important accelerators in rubber vulcanization. 

The intermediates M1-M5 were prepared according to the procedure described in Chap. 2. IIJ could be obtained by the treatment of 0,0-dimethyl l-(substimted phenoxyacetoxy)aIkylphosphonates IC with an excess of t-butylamine. In this reaction, t-butylamine could selectively and quantitatively eliminate one methyl from two MeO groups which attached to phosphorus in IC. The possible reaction mechanism for forming r-butylaminium 0-methyl phosphonate IIJ is outlined in Scheme 3.13. t-Butylamine first attacks the methyl carbon, forming intermediateiV-t-butyl-A-methyl ammonium salt, which is then deprotonated by another f-butyl-amine to form t-butylaminium and iV-methyl-Al-r-butylamine. Finally, the cation of t-butylaminium binds with the anion of phosphonate to form the IIJ. 

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 amines are a group of compounds with the general formula R-NHj, and all the common amines are hazardous. As a class the amines pose more than one hazard, being flammable, toxic, and, in some cases, corrosive. The amines are an analogous series of compounds and follow the naming pattern of the alkyl halides and the alcohols that is, the simplest amine is methyl amine, with the molecular formula of CH NHj. Methyl amine is a colorless gas with an ammonia-like odor and an ignition temperature of 806°F. It is a tissue irritant and toxic, and it is used as an intermediate in the manufacture of many chemicals. Ethyl amine is next in the series, followed by propyl amine, isopropyl amine, butyl amine and its isomers, and so on. 

Examination of the history of antioxidants such as hindered phenols and amines shows a move from low-MW products to higher-MW products. Specifically, polymer industries have abandoned the use of, e.g., butylated hydroxy toluene (BHT) in favor of tetrakismethylene (3,5-di-f-butyl-4-hydroxydrocinnamate)methane (see Figure 15.9). Likewise, polymeric HALS, like poly-methylpropyl-3-oxy-(4(2,2,6,6-tetramethyl)piperidinyl) siloxane, replaced the low-MW hindered amine Lowilite 77 (see Figure 15.10). The next obvious step was to produce a new class of stabilizers. 

SFC-FID is widely used for the analysis of (nonvolatile) textile finish components. An application of SFC in fuel product analysis is the determination of lubricating oil additives, which consist of complex mixtures of compounds such as zinc dialkylthiophosphates, organic sulfur compounds (e.g. nonylphenyl sulfides), hindered phenols (e.g. 2,6-di-f-butyl-4-methylphenol), hindered amines (e.g. dioctyldiphenylamines) and surfactants (sulfonic acid salts). Classical TLC, SEC and LC analysis are not satisfactory here because of the complexity of such mixtures of compounds, while their lability precludes GC determination. Both cSFC and pSFC enable analysis of most of these chemical classes [305]. Rather few examples have been reported of thermally unstable compounds analysed by SFC an example of thermally labile polymer additives are fire retardants [360]. pSFC has been used for the separation of a mixture of methylvinylsilicones and peroxides (thermally labile analytes) [361]. 

In an acetone extract from a neoprene/SBR hose compound, Lattimer et al. [92] distinguished dioctylph-thalate (m/z 390), di(r-octyl)diphenylamine (m/z 393), 1,3,5-tris(3,5-di-f-butyl-4-hydroxybenzyl)-isocyanurate m/z 783), hydrocarbon oil and a paraffin wax (numerous molecular ions in the m/z range of 200-500) by means of FD-MS. Since cross-linked rubbers are insoluble, more complex extraction procedures must be carried out (Chapter 2). The method of Dinsmore and Smith [257], or a modification thereof, is normally used. Mass spectrometry (and other analytical techniques) is then used to characterise the various rubber fractions. The mass-spectral identification of numerous antioxidants (hindered phenols and aromatic amines, e.g. phenyl-/ -naphthyl-amine, 6-dodecyl-2,2,4-trimethyl-l,2-dihydroquinoline, butylated bisphenol-A, HPPD, poly-TMDQ, di-(t-octyl)diphenylamine) in rubber extracts by means of direct probe EI-MS with programmed heating, has been reported [252]. The main problem reported consisted of the numerous ions arising from hydrocarbon oil in the recipe. In older work, mass spectrometry has been used to qualitatively identify volatile AOs in sheet samples of SBR and rubber-type vulcanisates after extraction of the polymer with acetone [51,246]. 

The kinetic resolution of racemic trans ester 76a using catalytic amounts of chiral amine-borane 78 and di-f-butyl peroxide as initiator under pho-tolytic conditions at - 74 °C provided the enantioenriched (R,R) product in 74% ee after 52% consumption of the racemate [64-67]. For the ester 76b, (R,R) product in 97% ee was isolated after 75% consumption at -90°C (Scheme 20). 

Amination of a-Uthiated derivatives of f-butyl acetate and a-phenylacetamide with la were reported to be unsuccessful. However, a-amino derivatives of Af-mono- and Af,Af-disubstimted carboxamides could be prepared by reaction of their a-lithiated derivatives with la (Scheme 12) . ... 

In order to eliminate the requirement of using at least 2 equivalents of RM (M = Li, MgBr) in their amination with the reagents 3i-o, e.g. 1 equivalent for the deprotonation of amino hydrogen and 1 equivalent for the amination reaction, A-metallated derivatives of 3i-o have been used. The lithium derivative of 31, e.g. A-lithio Af-(f-butoxycar-bonyl) 0-p-tosylhydroxylamine (A-lithio f-butyl A-tosyloxycarbamate), is also known as LiBTOC. 

In our NMR studies 143,147,148,322-324) of amine and other adducts of Ni[R-dtp]2 complexes neat amines were employed in order to eliminate variations in extent of association (H-bonding) of the amines, to permit observation of NH proton shifts, and to maximize the concentration of the preferred adduct. The use of high concentration of primary amines in solutions with Ni[R-dtp]2 complexes can lead to products other than those expected, e.g., with aliphatic diamines, the R-dtp anion salts of f/zs(diamine)nickel(ll) chelates are obtained ). Furlani and co-workers ) have shown that Ni-(ethyl-dtp)2 reacts with n-butyl amine to yield complexes containing the NiS2N4 chromophore, presumably with monodentate ethyl-dtp. In all work with adducts it is necessary to assure that the complexes, adduct molecules and solvent systems are anhydrous. A number of authors 132,284,295,329) shown that Ni[ R-dtp ]2 complexes decompose when in contact with water. 

In the presence of diisopropyl(ethyl)amine, tetrachlorosilane reacts with f-butyl hydroperoxide to give 1 1 adduct 9 (equation 16). Alkylperoxydiorganoalkoxysilanes are prepared from the reaction of chlorodiorganooxysilane with alkyl hydroperoxides in the presence of ammonia or organic base such as pyridine or triethylamine (equations 17 and 18). 

Trifluoroalanine has also been prepared by reducing trifluoropyruvate imines (ethyl trifluoropyruvate is available commercially it is prepared either from per-fluoropropene oxide or by trifluoromethylation of ethyl or f-butyl oxalate). These imines are obtained by dehydration of the corresponding aminals or by Staudinger reaction. They can also be obtained by palladium-catalyzed carbonylation of trifluoroacetamidoyl iodide, an easily accessible compound (cf. Chapter 3) (Figure 5.4). Reduction of the imines affords protected trifluoroalanines. When the imine is derived from a-phenyl ethyl amine, an intramolecular hydride transfer affords the regioisomer imine, which can further be hydrolyzed into trifluoroalanine. ... 

The results of some of the many aminations of pyridine and its derivatives that have been carried out appear in Table 14. Yields are quoted where possible but these should not be used for quantitative comparisons as reaction and work up conditions vary widely. 2-Alkylpyridines aminate at the vacant a-position, except when the substituent is very large. 2-f-Butylpyridine does not undergo the Chichibabin reaction, probably because the bulky 2-f-butyl group prevents adsorption on to the sodamide surface. In contrast, 2-phenylpyridine undergoes amination in very good yield. Aminations of 2- and 4-methyl-pyridines do not involve attack on the anhydrobases in aprotic solvents, but some ionization does take place in liquid ammonia. 4-Benzylpyridine forms a carbanion (148) which is only aminated with difficulty by a second mole of sodamide (equation 103). 

Enamines or imines can form pyridines by cyclization to a nitrile group, as shown in the production of compound (48). Alternatively, the nitrogen atpm of the nitrile can be made more nucleophilic by attack on the carbon atom by an external nucleophile. Ammonia causes cyclization of the dienamines (53) (77JHC1077) and (54) (78JAP(K)786878l) in both cases, elimination of the amine introduces the extra double bond. Dimethylamine or piperidine cause cyclization of l-cyano-2,5,5-trimethylhex-l-en-3-yne to the f-butyl-pyridine (55). There are a few other examples of the synthesis of bicyclic compounds from... 

Simple ketones and esters are inert. On the other hand, nitroalkanes react smoothly in f-butyl alcohol as a solvent with butadiene, and their acidic hydrogens are displaced with the octadienyl group. From nitromethane. three products, 64, 65, and 66, are formed, accompanied by 3-substituted 1,7-octadiene as a minor product. Hydrogenation of 65 affords a fatty amine 67 which has a primary amino function at the center of the long linear chain[46,61]. 

Hydroperoxides and peroxides oxidize primary and secondary aliphatic amines to imines. Thus f-butyl hydroperoxide oxidizes 4-methyl-2-pentyl-amine to 2-(4-methylpentylidene)-4-methyl-2-pentylamine in 66% yield [29]. Di-r-butyl peroxide reacts in a similar manner [29]. However, this reaction is... 

In the Sepracor synthesis of chiral cetirizine di hydrochloride (4), the linear side-chain as bromide 51 was assembled via rhodium octanoate-mediated ether formation from 2-bromoethanol and ethyl diazoacetate (Scheme 8). Condensation of 4-chlorobenzaldehyde with chiral auxiliary (/f)-f-butyl sulfinamide (52) in the presence of Lewis acid, tetraethoxytitanium led to (/f)-sulfinimine 53. Addition of phenyl magnesium bromide to 53 gave nse to a 91 9 mixture of two diastereomers where the major diasteromer 54 was isolated in greater than 65% yield. Mild hydrolysis conditions were applied to remove the chiral auxiliary by exposing 54 to 2 N HCl in methanol to provide (S)-amine 55. Bisalkylation of (S)-amine 55 with dichlonde 56 was followed by subsequent hydrolysis to remove the tosyl amine protecting group to afford (S)-43. Alkylation of (5)-piperizine 43 with bromide 51 produced (S)-cetirizine ethyl ester, which was then hydrolyzed to deliver (S)-cetirizine dihydrochloride, (5)-4. 

Primary alkyl amines RNH2 can be converted1045 to alkyl halides by (1) conversion to RNTs2 (p. 354) and treatment of this with I" or Br in DMF,347 (2) diazotization with f-butyl nitrite and a metal halide such as TiCl4 in DMF,1046 or (3) the Katritzky pyrylium-pyridinium method (p. 354).1,147 Alkyl groups can be cleaved from secondary and tertiary aromatic amines by concentrated HBr in a reaction similar to 0-68, e.g.,104,1... 

There is direct evidence, from ir and nmr spectra, that the f-butyl cation is quantitatively formed when f-butyl chloride reacts with A1CI3 in anhydrous liquid HCI.246 In the case of olefins, Markovnikov s rule (p. 750) is followed. Carbocation formation is particularly easy from some reagents, because of the stability of the cations. Triphenylmethyl chloride247 and 1-chloroadamantane248 alkylate activated aromatic rings (e.g., phenols, amines) with no catalyst or solvent. Ions as stable as this are less reactive than other carbocations and often attack only active substrates. The tropylium ion, for example, alkylates anisole but not benzene.249 It was noted on p. 337 that relatively stable vinylic cations can be generated from certain vinylic compounds. These have been used to introduce vinylic groups into aryl substrates.250... 

Enamines can be prepared from ot-cyano tertiary amines by treatment with KOH or f-BuOK in boiling benzene or toluene, or in f-butyl methyl ether at room temperature.262... 

Tertiary alkyl primary amines can be oxidized to nitro compounds in excellent yields with KMn04.39S This type of nitro compound is not easily prepared in other ways. All classes of primary amine (including primary, secondary, and tertiary alkyl as well as aryl) are oxidized to nitro compounds in high yields with dimethyldioxirane.399 Other reagents that oxidize various types of primary amines to nitro compounds are dry ozone,4,111 various peracids,401 including peracetic and peroxytrifluoroacetic acids, f-butyl hydroperoxide in the presence of certain molybdenum and vanadium compounds,402 F7-H20-MeCN,41123 and sodium perborate.403... 

The orf/to-formylation of 2-aminopyridines can be effected via the rearrangement of the azasulfonium salt prepared from a 2-aminopyridine, 1,3-dithiane, f-butyl hypochlorite and sodium methoxide (74CC685). The crude sulfilimine (815) was refluxed in f-butanol containing potassium f-butoxide to yield the dithioacetal (816). Hydrolysis of (816) with mercury(II) oxide/boron trifluoride etherate gave the aldehyde (817 Scheme 191). This method should be applicable to the formylation of other heterocyclic amines. 

A consequence of the addition of coordinated OH- to alkenes is that other nucleophilies, for example a coordinated aminate ion, should also be active. This type of reaction is seen with the chloropentaammine complex [Co(NH3)500CCH=CHC02Bu,]2+ in aqueous base533 (Scheme 49). The reaction of the f-butyl maleate complex occurs to the extent of ca. 50% and is complicated by hydrolysis of the maleate ester and some decomposition of the cobalt(III) complexes. Reactions of this type have recently been exploited in the synthesis of j3-carboxyaspartic acid in the coordination sphere of cobalt(III).53... 

Inclusion in the reaction of a cooxidant serves to return the osmium to the osmium tetroxide level of oxidation and allows for the use of osmium in catalytic amounts. Various cooxidants have been used for this purpose historically, the application of sodium or potassium chlorate in this regard was first reported by Hofmann [7]. Milas and co-workers [8,9] introduced the use of hydrogen peroxide in f-butyl alcohol as an alternative to the metal chlorates. Although catalytic cis dihydroxylation by using perchlorates or hydrogen peroxide usually gives good yields of diols, it is difficult to avoid overoxidation, which with some types of olefins becomes a serious limitation to the method. Superior cooxidants that minimize overoxidation are alkaline t-butylhydroperoxide, introduced by Sharpless and Akashi [10], and tertiary amine oxides such as A - rn e t h y I rn o r p h o I i n e - A - o x i d e (NMO), introduced by VanRheenen, Kelly, and Cha (the Upjohn process) [11], A new, important addition to this list of cooxidants is potassium ferricyanide, introduced by Minato, Yamamoto, and Tsuji in 1990 [12]. 

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