Amines from aliphatic

A simple method for the preparation of primary amines from aliphatic halides involves the treatment of the halide with KOCN in alcohol to give the urethane which is hydrolyzed to the amine. In general the yields are high. A novel conversion in which tetrakis(dimethylamino) titanium converts carboxylic acids and their common derivatives in orthoamides and ketene N,N-acetals in good yields is described. ... 

The behavior of aromatic amines with nitrous acid is characteristic. The reagent serves to distinguish not only primary, secondary, and tertiary amines from one another, but aromatic amines from aliphatic amines in the case of primary and tertiary compounds. 

Reduction of aldehydes and ketones allylic alcohols from a, 3-unsaturated aldehydes and ketones alcohols from carboxylic acid chlorides amines from aliphatic azides.21 ... 

The synthesis of primary amines in biphasic operation has been developed via selective reductive amination of aromatic and aliphatic carbonyl compounds using aqueous ammonia in the presence of water-soluble transition metal catalysts [17]. The use of [Rh(cod)Cl]2 with TPPTS as catalyst and ammonium acetate in water/ THF afforded benzylamine from benzaldehyde in 86% yield. This method is also feasible for the synthesis of aliphatic primary amines from aliphatic aldehydes in... 

Amines can often be induced to react with aromatic halides, in which activating influences of the type discussed above are absent, by employing the device of catalysis by copper and various copper compoimds (reactions 59 and 60). Diarylamines (from aromatic amines and mixed aliphatic-aromatic amines (from aliphatic amines are obtainable in this way. These induced reactions have... 

Aromatic primary amines differ markedly from aliphatic amines in their reaction with nitrous acid. Thus a cold aqueous solution of mono thylamine hydrochloride reacts with nitrous acid to give mainly the corresponding primary alcohol ... 

The reaction is applicable to the preparation of amines from amides of aliphatic aromatic, aryl-aliphatic and heterocyclic acids. A further example is given in Section IV,170 in connexion with the preparation of anthranilic acid from phthal-imide. It may be mentioned that for aliphatic monoamides containing more than eight carbon atoms aqueous alkaline hypohalite gives poor yields of the amines. Good results are obtained by treatment of the amide (C > 8) in methanol with sodium methoxide and bromine, followed by hydrolysis of the resulting N-alkyl methyl carbamate ... 

The method can be used to prepare a number of a-aminonitriles from aliphatic or aromatic aldehydes and ketones and secondary aliphatic amines.4... 

A variety of cleavage conditions have been reported for the release of amines from a solid support. Triazene linker 52 prepared from Merrifield resin in three steps was used for the solid-phase synthesis of aliphatic amines (Scheme 22) [61]. The triazenes were stable to basic conditions and the amino products were released in high yields upon treatment with mild acids. Alternatively, base labile linker 53 synthesized from a-bromo-p-toluic acid in two steps was used to anchor amino functions (Scheme 23) [62]. Cleavage was accomplished by oxidation of the thioether to the sulfone with m-chloroperbenzoic acid followed by 13-elimination with a 10% solution of NH4OH in 2,2,2-trifluoroethanol. A linker based on l-(4,4 -dimethyl-2,6-dioxocyclohexylidene)ethyl (Dde) primary amine protecting group was developed for attaching amino functions (Scheme 24) [65]. Linker 54 was stable to both acidic and basic conditions and the final products were cleaved from the resin by treatment with hydrazine or transamination with ra-propylamine. 

These authors also found that the addition of excess MgO during the in situ preparation of allyltantalum species improved reaction outcomes, even allowing for the first example of allylation of imines derived from aliphatic amines and aliphatic aldehydes (prepared in situ at room temperature in the presence of molecular sieves) (Equation (18)). The selective addition to imines permitted three-component reactions. 

The electrophiles in such reactions can be either aryl halides or triflates, possessing electron-rich, neutral or electron-poor ring systems, whereas amines can range from aliphatic to aromatic and primary to tertiary amines. The Pd-catalyzed C—N bond formation works both inter- and intramolecularly. 

The benzotriazole derivatives 101 (R1 = alkyl) formed from aliphatic aldehydes, ben-zotriazole and primary aromatic amines are reduced by lithium aluminium hydride or sodium borohydride to secondary amines 102, while Grignard reagents yield compounds of type 103116. The reaction has been used for the side-chain alkylation of 2-aminopyridine (equation 42) (direct alkylation occurs predominantly at the ring nitrogen atom). 

Conjugated arylalkenes undergo ally lie amination on treatment with /V-phcnylhydro-xylamine under the influence of iron phthalocyanin, e.g. equation 71. The yields from aliphatic olefins are very poor 1-octene gives only 3% of the amine 193198. 

Aliphatic c a -dibromo ketones, such as 2,4-dibromopentan-3-one (262), react with primary amines RNH2 (R = Me, Et, Pr, /-Pr or t-Bu) to give mixtures of imines 263 and lesser amounts of diimines 264. l,3-Dibromo-l-phenylpropan-2-one yields only the amide 265, the product of a Favorskii rearrangement. The nature of the products from aliphatic amines and cyclic a,a -dibromo ketones depends on ring size the cyclohexanone derivative 266 gave Favorskii amides 267 (R = Pr, /-Pr or t-Bu), while trans-2,5-dibromocyclopentanone afforded the enamines 268 (R = /-Pr or t-Bu) (equation 95)296. 

Primary aliphatic or aromatic amines RNH2 are converted into carbamates RNHCC Et on treatment with carbon monoxide and di-t-butyl peroxide in the presence of palladium(II) chloride and copper(II) chloride357. Carbamic esters 304 and 305 are also obtained from aliphatic amines and ortho carbonates (R30)4C358. Vinyl carbamates R12NC02CH=CHR2 are produced from secondary aliphatic amines, acetylenes R2C=CH (R2 = Bu or Ph) and carbon dioxide in the presence of ruthenium(III) chloride359. 

Combination of BP with 2-propanol or amines induces homopolymerization alone. The rate constants of BP 3 - isopropylamine and triethylamine are 2.95 10 and 2.42 1()9m-1s-1, respectively(22) whereas that of BP 3 - isooctane as a model of OPP is 1.0 lO M s l (24). Also hydrogen abstraction from 2-propanol(k=1.0 106 M s"1) (25) is much more efficient than that from aliphatic hydrocarbons. Even methanol is more reactive (k=2.8 10% - s - -) (25) than OPP towards BP 3. The aforementioned results and the finding that surface grafting does not occur in methanol are well interpreted by the following elementary reactions. 

Similar to the CuOTf/PyBox system, the CuBr/QUINAP system also gave high enantioselectivities of the three component reactions to construct propargyl amines from aldehydes, amines, and alkynes (Scheme 5.6). In this system various aldehydes including aromatic aldehydes and aliphatic aldehydes could be used and a wide range of chiral propargyl amines were prepared in good yields and enantioselectivities. Mechanistic studies showed that the dimeric Cu/QUINAP complex is the catalytically active species that differs from the previous reaction. 

Preparation of Propargylk Tertiary Amines from Propargyl Bromide and Aliphatic or Cycloaliphatic Secondary Amines... 

Schade, G. W., and P. J. Crutzen, Emission of Aliphatic Amines from Animal Husbandry and Their Reactions Potential Source of N20 and HCN, /. Atmos. Chem., 22, 319-346 (1995). 

A. Baiker u. J. Kijenski, Catal. Rev.-Sci. Eng. 27, 653-697 (1985) Catalytic Synthesis of higher Aliphatic Amines from the Corresponding Alcohols". 

---