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Amines olefinic amides

Reaction between secondary amines or amides and nitrous acid 5-30 Addition of NOC1 to olefins... [Pg.1294]

The Reaction of 2 with Amines or Amides. Two hundred mg of 2 was placed, under nitrogen, in a double Schlenk tube fitted with a reflux condenser and septum adapter. The amine or amide (5 ml) was added, and the mixture was placed in an oil bath preheated to 200°C. After the mixture turned black it was heated for an additional 20 min, cooled, and passed through the filter disc. This solution can be used directly for hydrogenation, or ether can be added to produce a Mack precipitate. The ether washed precipitate can also be used in olefin hydrogenations. [Pg.131]

Saturated hydrocarbons < olefins < aromatic hydrocarbons = organic halides < sulfides < ethers < nitro compounds < esters = aldehydes = ketones < alcohols = amines < sulfones < amides < carboxylic acids... [Pg.26]

The basic Markovnikov selectivity pattern is partially or fully overrun in the presence of neighboring coordinating groups within the olefin substrate (Section 2.2.2). Known functionalities where inversed selectivity can occur include 3-alke-noylamides (e.g. 17 reacts to give a mixture of 18 and 19, Table 3) [43], homoallyl esters and alcohols, allyl ethers (but not necessarily allyl alcohols) [44], allyl amines, allyl amides, or carbamates (cf. 20 to 21) [45], allyl sulfides [46] or 1,5-dienes [47]. As a matter of fact, aldehyde by-products are quite normal in Wacker reactions, but tend to be overlooked. [Pg.294]

Ruthenium-catalysed oxidations with dioxygen or hypochlorite are currently methods of choice for the oxidation of alcohol, ethers, amines and amides. In hydrocarbon oxidations, in contrast, ruthenium has not yet lived up to expectations. The proof of principle with regard to direct oxidation of, for example, olefins, with dioxygen via a nonradical, Mars-van Krevelen pathway has been demonstrated but this has, as yet, not led to practically viable systems with broad scope. The problem is one of rate although feasible the heterolytic oxygen-transfer pathway cannot compete effectively with the ubiquitous free-radical autoxidation. [Pg.316]

This ether is prepared by the Williamson ether synthesis from alcohols and phenols using a-bromomethylstyrene. It is cleaved by treating the ether in THF with f-BuLi at —78°C for 30 min (75-97% yield). The phenallyl ether can be cleaved in the presence of an allyl ether. Phenallyl amines and amides are cleaved similarly. Cleavage occurs by an addition of the alkyllithium to the olefin followed by elimination. [Pg.99]

Nickel boride is useful for selective reduction of olefins without hydrogenolysis of hydroxyl substituents or hydrogenation of carbonyl or epoxy groups also amines and amide groups are also unaffected . [Pg.166]

One of the useful application.s of NMR has been i/i the delerniitiation of functional groups, such as hy droxyl groups in alcohols and phenols, aldehydes, carboxylic acids, olefins, acetylenic hydiogeiis. amines, and amides. Relaiive errors in the range of I % to are reported. [Pg.529]

In the pesence of Mo(=CHCMe2Ph)(=NAr)[OCMe(CF3)2]2 the /-butoxycarbo-nyl (Boc)-protected amine, CH2=CHCH2NHC(0)0CMe3 (2 equiv in toluene), gives a 60% yield of the bis(Boc) amine after 8h (Marmo 1994). Attempts to metathesize olefinic amides with WCle-based catalysts were unsuccessful (Levisalles 1984). [Pg.144]

Organic residual components are the most worrying because of their toxicity. Some of these compounds are formed as by-products. Volatile organic compounds are determined by headspace GC, GC-MS. Intermediate products, such as sultones and sulfones, from sulfonation of olefin and alkyl-benzene, respectively, can be detected by LC. Unreacted products, like ethylene oxide from the synthesis of ethoxylated nonionic and anionic surfactants, are studied by GC benzyl chloride from the quaternization of tertiary amines and aliphatic amines from amidation reaction are determined by LC (Figure 5). [Pg.4721]

The Pd(ll)- and Pt(ll)-promoted nucleophilic additions to olefins are important reactions in organic synthesis. Nucleophiles that have been shown to add to coordinated olefins include OH , RO , AcO , CP, amines, and amides, and with the possible exception of OH", nucleophilic attack takes place on the side of the double bond remote from the metal. The main difference between Pd(ll)- or Pt(Il)-promoted and Fe(II)-promoted addition is that nucleophilic attack on Pd(ll)- or Pt(II)-coordinated monoolefins results in reduction of the divalent metal to the zero valent state. In most cases, Pd(ll) salts promote nucleophilic attack on olefins more readily than Pt(II) salts (Hartley, 1973 Maitlis, 1971). Equations (97) (Stern and Spector, 1961), (98) (Baird, 1966), (99) (Kitching et al., 1966), (100) (Akermark et al., 1974), and (101) (Kohl and Van Helden, 1968 Henry, 1972) illustrate some typical Pd(ll)- and Pt(II)-promoted additions to olefins. [Pg.37]

Several other jV-sulphinyl-amines or -amides can be prepared or generated, without isolation, and added to olefins,ketones, or enamines and ynamines. Similarly, A -sulphinyl-sulphonamides (1) and sulphinyl-amines (2 Ar = Ph or P-NO2C6H4) react with hexafiuoroacetone or polyfiuoro-olefins in aprotic solvents in the presence of CsF [see reactions (1) and (2)1, affording, directly, the imino-compounds these are undoubtedly formed via initial formation of the [2 + 2]-cyclo-adducts. ... [Pg.128]

Amines may also be prepared by conversion of olefins into amides followed by hydrolysis or reduction. See section 89 (Amides from Olefins) and section 96 (Amines from Amides)... [Pg.265]

The palladium catalyzed Heck reaction of 2-pyridyl tosylates would not only provide access to the a-arylated olefins but also act as direct precursors to the attractive chiral benzylic amine and amide derivatives often found in bioactive compounds. [Pg.85]

Metal-catalyzed oxidative addition of nitrogen nucleophiles such as amines and amides to olefins represents a straightforward atom economical approach for the preparation of enamines and enamides, respectively. These aminatimi processes may proceed with Markovnikov or anti-Markovnikov regioselectivity and in the latter case such products can be obtained as either or Z isomers (Scheme 1). Therefore, the ability of the catalyst to control that regiochemistry and stereoselectivity constitutes a chaUenging issue for synthetic chemists. [Pg.57]

Simple palladium(II) salts such as chloride and acetate efficiently catalyse aerobic oxidative A-alkylation of amines and amides with alcohols. This method is suitable for a variety of sulfonamides, amides, aromatic and heteroaromatic amines as well as benzylic and heterobenzylic alcohols with a low loadings of the catalyst (0.5-1 mol%) and the alcohols. A selective carbon-carbon double bond assisted o-C-H olefination is catalysed by palladium(II) acetate. The terminal oxidant is oxygen. Addition of TFA is essential for any meaningful yield. (PdOCOCF3)+ has been proposed as the active catalyst. The observed large difference in the inter- and intra-molecular KIE values implied that the coordination of the C=C bond occurs before C-H palladation in the catalytic cycle consequently, a mechanism involving the initial coordination of allylic C=C bond to (PdOCOCF3)+ followed by selective o-C-H bond metalation has... [Pg.130]

Sanyo [26] has reported a polymer composition that was found to be useful as a VI improver in mineral oils. This polymer composition consisted of an olefin copolymer, an olefin-methacrylate copolymer, and an oxyal-kylated alcohol or amine or amide-based smfactant. Sanyo [27] has also reported the use of polyolefm-graft-dimethylaminoethyl methacrylate copolymers as VI improvers. Copolymers of A-vinyl pyrrolidone and NJ -dialkylamino alkyl methacrylates were also reported as useful VI improvers by Sanyo [28]. [Pg.437]

Apparently the alkoxy radical, R O , abstracts a hydrogen from the substrate, H, and the resulting radical, R" , is oxidized by Cu " (one-electron transfer) to form a carbonium ion that reacts with the carboxylate ion, RCO - The overall process is a chain reaction in which copper ion cycles between + 1 and +2 oxidation states. Suitable substrates include olefins, alcohols, mercaptans, ethers, dienes, sulfides, amines, amides, and various active methylene compounds (44). This reaction can also be used with tert-huty peroxycarbamates to introduce carbamoyloxy groups to these substrates (243). [Pg.131]

Me3SiI, CH2CI2, 25°, 15 min, 85-95% yield.Under these cleavage conditions i,3-dithiolanes, alkyl and trimethylsilyl enol ethers, and enol acetates are stable. 1,3-Dioxolanes give complex mixtures. Alcohols, epoxides, trityl, r-butyl, and benzyl ethers and esters are reactive. Most other ethers and esters, amines, amides, ketones, olefins, acetylenes, and halides are expected to be stable. [Pg.180]


See other pages where Amines olefinic amides is mentioned: [Pg.178]    [Pg.178]    [Pg.124]    [Pg.205]    [Pg.546]    [Pg.1581]    [Pg.44]    [Pg.358]    [Pg.468]    [Pg.183]    [Pg.24]    [Pg.1580]    [Pg.156]    [Pg.119]    [Pg.2503]    [Pg.221]    [Pg.126]    [Pg.267]    [Pg.590]    [Pg.508]    [Pg.218]    [Pg.454]    [Pg.185]    [Pg.27]   
See also in sourсe #XX -- [ Pg.170 , Pg.199 ]




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