Olefins from amines

Silylated primary allylic amines, e.g. CH2=CHCH2N(SiMe3)2, are produced from allylic chlorides and the mixed reagent AgI/LiN(SiMe3)2205. The formation of allylic amines from olefins by the ene reaction is shown in equation 77. The ene adducts 205 from bis(2,2,2-trichloroethyl) azodicarboxylate are converted into 206 by zinc dust in acetone/acetic acid206. 

Aqueous organometalHc catalysis allows the use of NH3-solutions in water for the direct synthesis of amines from olefins in a combined hydroformylation/reductive amination procedure (Scheme 4.19). The hydroformylation step was catalyzed by the proven Rh/TPPTS or Rh/BINAS (44) catalysts, while the iridium complexes formed from the same phosphine ligands and [ IrCl(COD) 2] were found suitable for the hydrogenation of the intermediate imines. With sufficiently high NH3/olefin ratios (8/1) high selectivity towards the formation of primary amines (up to 90 %) could be achieved, while in an excess of olefin the corresponding... 

ALKANOLAMNES - AL KAN OL AMINES FROM OLEFIN OXIDES AND AMMONIA] (Vol 2)... 

White, R.W. King, S.W. O Brien, J.L. Catalytic reduction of ozonides. 11. Synthesis of amines from olefins. Tetrahedron Lett. 1971,12, 3591-3593. 

Amides may also be prepared by conversion of olefins into amines followed by acylation. See section 104 (Amines from Olefins)... 

For molecules similar to safrole or allylbenzene we take the work done on any terminal alkene such as 1-heptene, 1 octene. Another term to look for is olefin which is a term for a doublebond containing species. What we then look for are articles about these olefins where the functional groups we are looking for are formed. Articles with terminology like methyl ketones from (P2P), ketones from , amines from etc. Or when we want to see about new ways to aminate a ketone (make final product from P2P) we look for any article about ketones where amines are formed. Sound like science fiction to you Well, how do you think we came up with half the recipes in this book It works ... 

Synthesis of the title compound is representative of a number of syntheses of nonaromatic nitrogen heterocycles via Pd(Ill-catalyzed amination of olefins. These tosylated enamines are not readily available by standard synthetic methods, and show potential for further functionalization of the heterocycle. The saturated amine can be synthesized from the title compound by hydrogenation of the double bond followed by photolytic deprotection. ... 

Iodosobenzene diacetate is used as a reagent for the preparation of glycol diacetates from olefins,9 for the oxidation of aromatic amines to corresponding azo compounds,10 for the ring acetylation of N-arylacetamides,11 for oxidation of some phenols to phenyl ethers,12 and as a coupling agent in the preparation of iodonium salts.13 Its hydrolysis to iodosobenzene constitutes the best synthesis of that compound.14... 

From a thermodynamic point of view, the addihon of NH3 and amines to olefins is feasible. For example, the free enthalpy for the addihon of NH3 to ethylene is AG° -4 kcal/mol [14]. Calculations showed that the enthalpies for the hydroamination of higher alkenes are in the range -7 to -16 kcal/mol and that the exothermicities of both hydrahon and hydroaminahon of alkenes are closely similar [15]. Such N-H addihons, however, are characterized by a high activation barrier which prevents the... 

Teter et al. filed a series of patents aimed at the production of organic compounds containing nitrogerf or the production of nitriles and amines from ammonia and olefins by passing mixtures of olefin and NH3 over transition metals, mainly cobalt deposited on various supports at 250-370°C and 100-200 bar [27- 3]. With cobalt on asbestos, a mixture of amine, nitrile, olefin hydrogenation product, polymers, and cracking products is obtained (Eq. 4.1) [31]. 

A more convenient, but less general, synthesis of diorganozincs from olefins is the nickel-catalyzed hydrozincation, shown in Scheme 6. The yields (40-63%) are independent of the amount of diethylzinc added, but dependent on the nature of the olefin. For allylic and homoallylic alcohols and amines, yields as high as 85-95% are possible.32,33... 

Asymmetric catalytic reduction reactions represent one of the most efficient and convenient methods to prepare a wide range of enantiomerically pure compounds (i.e. a-amino acids can be prepared from a-enamides, alcohols from ketones and amines from oximes or imines). The chirality transfer can be accomplished by different types of chiral catalysts metallic catalysts are very efficient for the hydrogenation of olefins, some ketones and oximes, while nonmetallic catalysts provide a complementary method for ketone and oxime hydrogenation. 

Abstract Aldehydes obtained from olefins under hydroformylation conditions can be converted to more complex reaction products in one-pot reaction sequences. These involve heterofunctionalization of aldehydes to form acetals, aminals, imines and enamines, including reduction products of the latter in an overall hydroaminomethylation. Furthermore, numerous conversions of oxo aldehydes with additional C.C-bond formation are conceivable such as aldol reactions, allylations, carbonyl olefinations, ene reactions and electrophilic aromatic substitutions, including Fischer indole syntheses. 

The present preparation of methylenecyclohexane is an example of an amine oxide pyrolysis. This route from amines to olefins in many cases yields pure olefins where the alternative method, the Hofmann exhaustive methylation reaction, is accompanied by some rearrangement to more stable isomeric olefins. 

Antistatic agents - [ALKANOLAMINES - ALKANOLAMINES FROM OLEFIN OXIDES AND AMMONIA] (Vol 2) - [ALKANOLAMINES - ALKANOLAMINES FROM OLEFIN OXIDES AND AMMONIA] (Vol 2) - [AMINE OXIDES] (Vol 2) - [ANTISTATIC AGENTS] (Vol 3) - [AMINES-FATTY AMINES] (Vol 2) - [PHOSPHORUSCOMPOUNDS](Voll8) -castor oil derivatives as [CASTOR OIL] (Vol 5) -from polyammes pIAMINES AND HIGHER AMINES ALIPHATIC] (Vol 8) -in styrene plastics [STYRENE PLASTICS] (Vol 22) -for textiles [SUGAR ALCOHOLS] (Vol 23)... 

Fabric softeners - [ALKANOLAMOSIES - ALKANOLAMINES FROM OLEFIN OXIDES AND AMMONIA] (Vol 2) - [AMINES - FATTY AMINES] (Vol 2) - [SUGARALCOHOLS] (Vol 23) -from polyamines [DIAMINES AND HIGHER AMINES ALIPHATIC] (Vol 8)... 

The reaction under consideration is typified by the formation of saturated carboxylic acids from olefins, carbon monoxide, and water. Other compounds have been used in place of olefins (alkyl halides, alcohols), and besides water, a variety of compounds containing active hydrogen may be employed. Thus, alcohols, thiols, amines, and acids give rise to esters, thio-esters, amides, and acid anhydrides, respectively (15). If the olefin and the active hydrogen are part of the same molecule, three or four atoms apart, cyclizations may occur to produce lactones, lactams, imides, etc. The cyclizations are formally equivalent to carbonylations, however, and will be considered later. 

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