Big Chemical Encyclopedia

Chemical substances, components, reactions, process design ...

Articles Figures Tables About

Ethers selectivity

Lewis acids are also used in conjunction with acyl halides. The reagent Nal—BF3 etherate selectively cleaves ethers in the order benzylic ethers > alkyl methyl ethers > aryl methyl ethers. [Pg.520]

Other coordination modes of trans-diammac have been identified where one (154) or both (155) primary amines are free from the metal.721 725 An extension of this concept involves attachment of active functional groups such as crown ethers selectively at one primary amine to generate ditopic ligands capable of electrochemically sensing alkali metal ions through their inductive effect on the Co11111 redox potential. One example is provided by (156) further, the 15-crown-5 and 18-crown-6 analogs were also prepared.726... [Pg.63]

C. On Fe-Beta-300 the dimethyl ether selectivity was maximum at 240 °C and the hydrocarbons (mostly LC4) selectivities increased in addition to some constant amount of formaldehyde between 240-360 °C (Fig. la). This result confirms the presence of light Bronsted and Lewis acid sites (Fig. 2a) in accordance with FTIR results by pyridine [6], The methyl iodide started to convert to hydrocarbon (C1-C4) at 240 °C but dimethyl ether was not detected. [Pg.343]

The liquid-phase dehydration of 1-hexanol and 1-pentanol to di-n-hexyl ether (DNHE) and di-n-pentyl ether (DNPE), respectively, has been studied over H-ZSM-5, H-Beta, H-Y, and other zeolites at 160-200°C and 2.1 MPa. Among zeolites with a similar acid sites concentration, large pore H-Beta and H-Y show higher activity and selectivity to ethers than those with medium pores, although activity of H-ZSM-5 (particularly in 1-pentanol) is also noticeable. Increased Si/Al ratio in H-Y zeolites results in lower conversion of pentanol due to reduced acid site number and in enhanced selectivity to ether. Selectivity to DNPE is always higher than to DNHE... [Pg.361]

The cobalt(I) complex CoBr(PPh3)3 as a boron trifluoride etherate selectively hydrogenates conjugated dienes to monoenes via an unusual 1,2-hydrogen addition at the more-substituted double bond (186). [Pg.334]

If we consider the generation of alkoxycarbenium ions by C-H bond dissociation, ethers should be of our first choice as precursors of alkoxycarbenium ions by analogy to carbamates. The oxidation potentials of ethers, especially aliphatic ethers, however, are very positive, and therefore, it is rather difficult to oxidize ethers selectively under usual conditions. The regioselectivity is also a problem. Usually a mixture of two regioisomers of products is obtained because two regioisomeric alkoxycarbenium ions are generated. [Pg.214]

These selectivities obtained with Amberlyst-15 seem to be rather optimistic in view of recent work, where only with overstoichiometric ratios high di-+tri-ether selectivity is obtained. It is also not settled why addition of tert-butanol to the reaction mixture suppresses isobutene oligomerization selectivity [34, 35], At this stage it should also be stressed that the tert-butylglycerol ethers (TBGE) mentioned are excellent substitutes for MTBE (ETBE) as gasoline octane boosting components [36]. [Pg.229]

Problem 14.12 Use any needed starting material to synthesize the following ethers, selecting from among intermolecular dehydration, Williamson synthesis, and alkoxymercuration-demercuration. Justify your choice of method. [Pg.295]

Since the acetoxy and methoxy synthetic derivatives exhibited herbicidal activity, we were curious whether this also occurred with other esters and ether derivatives of 1 and its isomer, 3,7-dimethyl-6-hydroxy-8-methoxyisochroman (4). We reasoned that 3,7-dimethyl-6,8-dimethoxyisochroman (3) represents a logical precursor for the systematic preparation of the desired ester and ether analogs of isochromans 1 and 4. To test this conjecture, we needed both an efficient synthesis of bis-ether 3 and a practical way to demethylate the C(6) or C(8) ethers selectively. [Pg.72]

Another fine distinction among salt catalysts was obtained by following the activity and olefin/ether selectivity of metal sulphates in the dehydration of ethanol and 1-propanol. A linear correlation between the electronegativity of the metal ion and the activity has been found, but the selectivity gave a curve with a minimum [51]. [Pg.295]

Cleavage of ethers. A few reports have mentioned that acyl iodides can cleave ethers in the absence of a Lewis acid. Since acyl iodides are not readily available, Oku et al. have used Nal and an acyl chloride as a possible equivalent. In any case, the system does cleave both cyclic and acyclic ethers selectively at the less substituted a-C—O bond. Although any acyl chloride can be used, use of pivaloyl chloride is particularly attractive because the resulting pivaloyl esters are readily hydrolyzed. Indeed this system is particularly useful for deprotection of methyl ethers. [Pg.587]

Iodonium salts 46 have been proposed as the reactive intermediates in several synthetically useful carbon-carbon bond forming reactions [1,40]. Reactions of adducts 46 with various silyl enol ethers selectively afford 1,4-diones, while the reactions with alkenes lead to the products of alkylation at the allylic position (Scheme 22) [40]. [Pg.108]

Next the generated secondary alcohol is protected as triisopropylsilylether using TIPSOTf. The greater bulk of the TIPS group makes it more stable than the TBS group towards acidic hydrolysis therefore reaction with 5 % H2SO4 cleaves the TBS ether selectively to yield 11. [Pg.167]

Crown ethers selectively complex various alkali metal cations and can be thus used as model systems to study interactions between a macrocycle-bound cation and the 7r-system of a sidearm arene. Alkali-metal cation-7i interactions have recently received considerable attention because of the biological importance [88, 89, 175]. These studies have focused on Na+ and K+ interacting with benzene, phenol, and indole, which are the side chain arenes of phenylalanine, tyrosine, and tryptophan, respectively. Recent work [177-180] has demonstrated the formation of stable complexes between, for example, K+... [Pg.110]

In the two-step process, the second-stage reactor is similar to the first-stage reactor but is packed with an optimized catalyst for aldehyde oxidation, based on Mo V oxides, and is run under different operating conditions. Care must be exercised during the separation and purification phases to avoid conditions favouring acrylic acid polymerization, e.g., by addition of a radical polymerization inhibitor such as the hydroquinone monomethyl ether. Selectivities to acrylic acid are higher than 90% at total conversion of the aldehyde. Overall yields referred to propylene are in the range 75-85%. Most acrylic acid produced is esterified for the production of acrylate esters. [Pg.54]

This vanadium method enables the cross-coupling only in combinations of silyl enol ethers having a large difference in reactivity toward radicals and in their reducing ability. To accomplish the crosscoupling reaction of two carbonyl compounds, we tried the reaction of silyl enol ethers and a-stannyl esters based on the following consideration. a-Stannyl esters (keto form) are known to be in equilibrium with the enol form such as stannyl enol ethers, but the equilibrium is mostly shifted toward the keto form. When a mixture of an a-stannyl ester such as 45 and a silyl enol ether is oxidized, it is very likely that the stannyl enol ether will be oxidized preferentially to the silyl enol ether. The cation radical of 45 apparently cleaves immediately giving an a-keto radical, which reacts with the silyl enol ether selectively because of the low concentration of the stannyl enol... [Pg.60]

Platas, C., Avecilla, R, de Bias, A., et al. (2001) A Schiff-base bibracchial lariat ether selective receptor for lanthanide(lll) ions. Journal of the Chemical Society, Dalton Transactions, 1699. [Pg.524]

Tritylone alcohol reacts readily with alcohols to give tritylone ethers. Selective reaction of primary alcohols in the presence of secondary alcohols is possible. These new ethers are more stable to acid than trityl ethers. They can be cleaved by Wolff Kishner reduction. ... [Pg.378]

U (a) Ether Selective extraction of UQ under certain conditions... [Pg.251]

Zinc-modified cyanoborohydride, prepared from anhydrous zinc chloride and sodium cyanoborohy-dride in the ratio 1 2 in ether, selectively reduced aldehydes and ketones but not acids, anhydrides, esters and tertiary amides. In methanol the reactivity paralleled the unmodified reagent. Zinc and cadmium borohydrides form solid complexes with DMF, which may prove to be convenient sources of the reducing agents.Aromatic and a,p-unsaturated ketones were reduced much more slowly than saturated ketones, so chemoselective reduction should be possible. [Pg.18]

As a class alkynes are much more reactive in hydroalumination than are alkenes. Hence, both terminal and internal alkynes react at feasible rates with both dialkylaluminum hydrides in alkanes and lithium aluminum hydrides (LiAlRnH4-n) in ethers. Selected examples of such additions are presented in Table 2. With alkyl or aryl substituents, it should be noted that R2AIH adds in a kinetically syn manner, (5 equation 2) and (7 equation 3), and LAH yields the anti adduct (14 equation 6). [Pg.740]


See other pages where Ethers selectivity is mentioned: [Pg.764]    [Pg.229]    [Pg.71]    [Pg.215]    [Pg.610]    [Pg.169]    [Pg.192]    [Pg.389]    [Pg.91]    [Pg.256]    [Pg.240]    [Pg.214]    [Pg.315]    [Pg.167]    [Pg.444]    [Pg.308]    [Pg.279]    [Pg.434]    [Pg.444]   
See also in sourсe #XX -- [ Pg.238 ]

See also in sourсe #XX -- [ Pg.238 ]

See also in sourсe #XX -- [ Pg.7 , Pg.238 ]

See also in sourсe #XX -- [ Pg.7 , Pg.238 ]

See also in sourсe #XX -- [ Pg.238 ]




SEARCH



© 2024 chempedia.info