Primary Aliphatic Amines and Diamines

T0144 Carus Chemical Company, CAIROX Potassium Permanganate 

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Primary Aliphatic Amines and Diamines Hexylamine Monomethylamine Primary Aliphatic Amines Pyridine and Substituted Pyridines Paraquat... 

Heterocyclic Sulfur Compounds with Two or More Rings Hexachlorobenzene under Ring-Substituted Aromatics Hexachlorobutadiene under Unsaturated Alkyl Halides Hexachlorocyclohexane Lindane under Saturated Alkyl Halides Hexachlorocyclopentadiene under Unsaturated Alkyl Halides Hexachloroethane under Saturated Alkyl Halides Hexadecane under Alkanes and Cyclic Alkanes Hexafluoroethane under Saturated Alkyl Halides Hexamethyldisihzane under Silicon Compounds—Other Significant Hexanes under Alkanes and Cyclic Alkanes Hexylamine under Primary Aliphatic Amines and Diamines... 

Monomethylamine under Primary Aliphatic Amines and Diamines... 

Primary Aliphatic Amines under Primary Aliphatic Amines and Diamines Propane under Alkanes and Cyclic Alkanes... 

Using this protocol, primary aliphatic amines, secondary aliphatic amines, and diamines could be converted into the corresponding urea derivatives in moderate yields. Additionally, catalytic efficiency of cations derived from various bases decreases in the order of > diamines > primary amines > secondary amines > aniline, probably being due to the steric effect and basicity. The catalyst could also be recovered after a simple separation procedure, and reused over five times with retention of high activity. This process presented here could show much potential application in industry due to its simplicity and ease of catalyst recycling. 

The addition of ammonia, primary and secondary amines to the nitrile group proceeds well if electron-attracting groups are present in the a-position to the nitrile function. Thus it is well known that amines add rapidly to trihaloacetonitriles or cyanogen to give amidines (317) and (318) respectively (Scheme 51). Recently it was reported that the addition of aliphatic amines and diamines to aliphatic or aromatic nitriles, respectively, proceeds with good yields if lanthanide triflates are present as catalysts. ... 

Primary (R = H) and secondary aromatic amines react with alkenes in the presence of thallium(III) acetate to give vie- diamines in good yields. " The reaction is not successful for primary aliphatic amines. In another procedure, alkenes can be diaminated by treatment with the osmium compounds R2NOSO2 and R3NOSO (R = t-Bu)," analogous to the osmium compound mentioned at 15-51. The palladium-promoted method of 15-51 has also been extended to diamination. " Alkenes can also be diaminated indirectly by treatment of the aminomercurial compound mentioned in 15-51 with a primary or secondary aromatic amine. 

In this study we examine the generalities in reductive alkylation however, since the subject is vast, we limited ourselves to the interaction of aromatic and aliphatic primary amines and diamines with ketones. The ketones examined include the cyclic ketone, cyclohexanone, and aliphatic ketones such as acetone, and methyl isobutyl ketone (MIBK). We limited our study to sulfided and unsulfided Pt and Pd catalysts supported on activated carbon that were commercially available from Evonik Degussa Corporation. 

While primary aliphatic amines are converted to nitro compounds on reaction with ozone these reactions are accompanied by numerous by-products.Such side-reactions are largely suppressed by first dissolving the amine onto silica gel followed by passing a stream of 3 % ozone in oxygen through the solid at -78 °C under anhydrous conditions, where yields of between 60 and 70 % are reported. This route has been used to synthesize the energetic cyclopropane (65) from the diamine (64) (Table 1.7). ... 

In a similar transformation of ylidene 104, obtained from Appel salt 20 and Meldrum s acid, with primary aliphatic amines, the reaction has been stopped at the stage of (alkylamino)cyanomethylidene 105 <2000J(P1)3107>. Ethylene diamine and other diamines gave under the same conditions imidazolidin-2-ylidenes... 

The reactions of nucleophilic substitution with participation of reactive clathrochelates are very sensitive to the donor properties of an attacking amine. With aromatic amines, as well as secondary and primary sterically hindered amines in acceptor solvents, and hexachloride precursors, the reaction stops with the formation of disubstituted products. When secondary and sterically hindered primary aliphatic amines are used in donor solvents and sterically unhindered primary aliphatic amines in acceptor solvents, the reaction terminates at trisubstituted products. In the case of sterically unhindered aliphatic amines, tetrasubstituted clathrochelates are formed. With dichloride precursor FeBd2(C12Gm)(BF)2, the primary aliphatic amines in donor solvents form diamine clathrochelates, whereas the secondary amines (diethylamine or piperazine) give only monoamine complexes both in acceptor and donor solvents. 

In the case of primary aliphatic amines, the reaction products are dramatically affected by the solvent employed. For instance, in the presence of solvents apt to produce a specific solvation of amines (chloroform, and an amine chlorohydrate solution in methylene dichloride), the reaction with hexachloride precursors terminates to yield the trisubstituted product DD D" formed via route A. At the same time, the use of some other solvents (such as benzene, 1,4-dioxane, THF, methylene dichloride, DMF, and alcohols, or the corresponding amine media) led to the formation of the sole tetrasubstituted product (DD"D"). In addition, in the case of sterically unhindered primary amines an alternative isomer (D D D") is not isolated, which indicates reaction route A and a specific control of the tie reaction in the transition state by solvation interactions and intramolecular hydrogen bonds. In the case of the dichloride FeBd2(C12Gm)(BF)2 precursor, with both primary (cyclohexylamine) and secondary (diethylamine and piperazine) aliphatic amines, only a monosubstituted product of the Bd2D type is formed in chloroform, whereas in some other solvents, a diamine clathrochelate of the Bd2D" type is obtained with both sterically hindered and unhindered primary aliphatic amines. 

A particularly strong browning-effect is achieved when ammonia is applied, because e reaction time is shortened and the reaction temperature decreased. - " Aliphatic primary and secondary amines and diamines may replace ammonia in these reactions, because of their catalytic effect, but they are not on the list of permitted additives. Thus, Gow Chih Yen studied such reactions from the point of view of produdng the most inten-... 

Condensing agents are basic catalysts such as alkali carbonates, hydrogen carbonates, hydroxides, or alkoxides, or primary aliphatic amines or calcium hydroxide zinc chloride may also be used with aromatic aldehydes. Ethylene-diamine was introduced by Lerner972 for use in the synthesis of unsaturated nitriles in the aromatic series and he gave a large number of examples in which yields were around 95%. 

The glycidyl adducts are, however, skin irritants, being akin to the parent amines in this respect. Substitution of the hydroxyethyl group and its alkyl and aryl derivatives at the nitrogen atom is effective in reducing the skin sensitization effects of primary aliphatic amines. Both ethylene and propylene oxides have thus been used in the preparation of adducts from a variety of amines, including ethylene diamine and diethylenetriamine. 

In (6-6)bicyclic aromatic systems photolysis of a-azido compounds in primary aliphatic amines favors azepine formation, while )S-azido compounds form o-diamines. o-Diamine formation again predominates in photolysis of both a- and j -azido(6-6)bicyclic aromatics in secondary aliphatic amines. This difference in behavior of a-azido-arenes may be accounted for by considering Scheme 2. 

The matrix polymer consisted of a system (Baytech from Bayer Ag) and the polyol was a polyether compound containing small amounts of tertiary aliphatic amine and a primary aromatic diamine and with an added activator. The isocyanate was a polyether-toluene di-isocyanate (TDI) prepolymer with isocyanate groups. 

Dehydrofluorination by primary and secondary aliphatic amines occurs at room temperature and is the basis of diamine cross linkmg, which occurs by dehydrofluonnation and subsequent nucleophihc substitution of the double bond The locus of dehydrofluonnation is a VDF unit flanked by two perfluoroolefin units This selectively base-sensitive methylene group also undergoes elimination as the first step in phase-transfer-catalyzed cross-hnking with quaternary ammo mum or phosphomum salts, bisphenols, and morganic oxides and hydroxides as HF acceptors [31, 32]... 

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