Amine secondary-alcohol

H-Bond Acceptor-Donor (HBAD) Phenols Aromatic acids Aromatic amines Alpha H nitriles Iniines Monocarboj hc acids Other monoacids Peracids Alpha H nitros Azines Primary amines Secondary amines n-alcohols Other alcohols Ether alcohols... 

Like alcohols, amines with fewer than five carbon atoms are generally water-soluble. Also like alcohols, primary and secondary amines form hydrogen bonds and are highly associated. As a result, amines have higher boiling points than alkanes of similar molecular weight. Diethylamine (MW = 73 amu) boils at 56.3 °C, for instance, while pentane (MW = 72 amu) boils at 36.1 °C. 

Schiffbase, 1147 Scurvy vitamin C and, 772 sec-Butyl group, 84 Second-order reaction, 363 Secondary alcohol, 600 Secondary amine, 917 Secondary carbon, 84 Secondary hydrogen. 85 Secondary structure (protein), 1038-1039... 

Aldehydes, formates, primary, and secondary alcohols, amines, ethers, alkyl halides, compounds of the type Z—CH2—Z, and a few other compounds add to double bonds in the presence of free-radical initiators/ This is formally the addition of RH to a double bond, but the R is not just any carbon but one connected to an oxygen or a nitrogen, a halogen, or to two Z groups (defined as on p. 548). The addition of aldehydes is illustrated above. Formates and formamides " add similarly ... 

Aldehydes hydric alcohols. and secondary alkyl amines... 

The addition of alkoxides to 2-nitro-l-phenylthio-l-alkenes affords P-nitro-aldehyde acetals.276 The reaction of the same nitroalkenes with amines gives nitroenamines.270 They are important intermediates for organic synthesis and are generally prepared by the reaction of nitroalkanes with triethylorthoformate in the presence of alcohols or secondary amines.2"1 0 The methods of Eqs. 4.20 and 4.21 have some merits over the conventional methods, for variously substituted (3-nitro-aldehydes acetals or nitroenamines are readily prepared by these methods. 

Transition-metal- and enzyme-catalyzed alkylations of ammonia and amines with alcohols and diols have been reviewed59. RuCl2(PPh3)3 is a homogeneous catalyst for the reaction of long-chain terminal alcohols with secondary amines to give tertiary amines (equation 22)60. 

Carboxylic acid, aldehyde, ketone, ether, alcohol, ester, ester-R (the chain attached to the oxygen atom being a generic substituent), anhydride, acetal, amide, epoxide, acid halyde, primary amine, primary imine, cyano, secondary amine, secondary imine, tertiary amine, nitro derivative, metal-1, metal-2, carbene, halo derivative. 

Although the chemistry of pentatetraenylidene complexes [M]=C(=C)3=CR R has not received as much attention as that of aUenylidenes, there is ample experimental evidence to confirm the electrophilic character of the C, Cy and carbons of the cumulenic chain [26-29, 31]. Thus, treatment of tra s-[RuCl(=C=C=C=C=CPh2) (dppe)2][PFg] (132) with alcohols or secondary amines resulted in addition of the nucleophilic solvent across the Cy=Cs double bond to give alkenyl-allenylidenes 138 (Scheme 48) [358]. In chloroform, electrophilic cyclization with one of the Ph groups occurred to give 139. This transformation is actually the parent of the later observed allenylidene to indenylidene intramolecular rearrangement (Scheme 15). 

However, alcohols or secondary amines usually add to the C3=C4 bond of pentatetraenylidene complexes of mthenium generated in situ and the finally isolated products are the corresponding alkenylallenylidene complexes. 

Propanol, 2 Isopropyl Alcohol Isopropanol Secondary Alcohols Secondary Aliphatic Amines... 

Version B In the case of an (7fi-PBA ester (amide) of a secondary alcohol (amine) of absolute configuration (Ljh L,) the H-NMR signal of L appears at a higher field and that of L2 at a lower field than in the corresponding (5)-PBA derivative. 

For other methods of converting certain alcohols to secondary and tertiary amines, see Murahashi Kondo Hakata Tetrahedron Lett. 1982, 23. 229 Baiker Richarz Tetrahedron Lett. 1977, 1937. Heh. Chim. Acta 1978, 61, 1169, Synth. Common 1978,8. 27 Grigg Mitchell Sutthivaiyakit Tongpenyai 7 Chem. Soc., Chem. Commun 1981, 611 Arcelli Bui-The-Khai Porzi J. Organomel. Chem. 1982,235, 93 Kelly Eskcw Evans 7. Org. Chem. 1986, 51. 95 Huh Tsuji Kobayashi Okuda Watanabc Chem. Lett. 1988, 449. 

Similarly, like secondary and tertiary alcohols, amines with the alkyl groups branched ona-carbon atoms (i.e. containingthe grouping R R2CH—... 

The [3-hydroxy amines are a class of compounds falling within the generic definition of Eq. 6A.6. When the alcohol is secondary, the possibility for kinetic resolution exists if the Ti-tartrate complex is capable of catalyzing the enantioselective oxidation of the amine to an amine oxide (or other oxidation product). The use of the standard asymmetric epoxidation complex (i.e., T2(tartrate)2) to achieve such an enantioselective oxidation was unsuccessful. However, modification of the complex so that the stoichiometry lies between Ti2 (tartrate) j and Ti2(tartrate)1 5 leads to very successful kinetic resolutions of [3-hydroxyamines. A representative example is shown in Eq. 6A.11 [141b,c]. The oxidation and kinetic resolution of more than 20 secondary [3-hydroxyamines [141,145a] provides an indication of the scope of the reaction and of some... 

Acetylketene (MeC0CH=C=0)—generated by flash photolysis—showed the following selectivities towards functional groups amines > alcohols (primary > secondary > tertiary) aldehydes ketones.19 The results accord with the ah initio calculations, which suggest planar, pseudo-pericyclic transition states. An imidoylketene, PrN=C(Me)CH=C=0, was also generated and showed similar selectivities. 

Reaction kinetics with the various reagents becomes faster as their nucleophilicity is increased. The following order of reactivity can be given primary aliphatic amine > primary aromatic amine > secondary aliphatic amine primary alcohol > secondary alcohol > water > tertiary alcohol phenol > mercaptan. 

In the reductive alkylation of ammonia with cyclohexanone, Skita and Keil found that, although cyclohexylamine was obtained in 50% yield over a nickel catalyst, over colloidal platinum dicyclohexylamine was produced as the predominant product even in the presence of an excess molar equivalent of ammonia. Steele and Rylander compared the selectivity to primary amine, secondary amine, and alcohol in the reductive alkylation of ammonia with 2- and 4-methylcyclohexanones over 5% Pd-, 5% Rh-, and 5% Ru-on-carbon as catalysts.18 As seen from the results shown in Table 6.2, the formation of secondary amine is greatly depressed by the methyl group at the 2 position. Thus over Pd-C the secondary amine was formed predominantly with cyclohexanone and 4-methylcyclohexanone while the primary amine was produced in 96% selectivity with 2-methylcyclohexanone. Over Ru-C the alcohol was formed quantitatively with 4-methylcyclohexanone without the formation of any amines, whereas with 2-methylcyclohexanone the alcohol was formed only to an extent of 57%, accompanied by the formation of 4 and 39% of the secondary and primary amines, respectively. These results indicate that secondary amine formation is affected by the steric hindrance of the methyl group to a much greater extents than is the formation of the primary amine or the alcohol. The results with Ru-C and Rh-C also indicate... 

Catalyst Primary Amine Secondary Amine Alcohol (%y... 

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