Ammonium cyclic ether

Halogens are frequently used as oxidation agents and, under two-phase conditions, they can either be employed as ammonium complex halide salts [3], or in the molecular state with or without an added quaternary ammonium catalyst [4]. Stoichiometric amounts of tetra-n-butylammonium tribromide under pH controlled conditions oxidize primary alcohols and low-molecular-weight alkyl ethers to esters, a,cyclic ethers produce lactones [3], and secondary alcohols yield ketones. Benzoins are oxidized to the corresponding benzils (80-90%) by the tribromide salts in acetonitrile in the presence of benzoyl peroxide [5]. 

The initiator used is important for copolymerizations between monomers containing different polymerizing functional groups. Basic differences in the propagating centers (oxonium ion, amide anion, carbocation, etc.) for different types of monomer preclude some copolymerizations. Even when two different monomer types undergo polymerization with similar propagating centers, there may not be complete compatibility in the two crossover reactions. For example, oxonium ions initiate cyclic amine polymerization, but ammonium ions do not initiate cyclic ether polymerization [Kubisa, 1996]. 

The other limitation stems from very different structure of heterocyclic monomers and thus very different reactivity of resulting active species. As already discussed, oxonium ions may initiate the polymerization of cyclic amines, but ammonium ions would not initiate the polymerization of cyclic ethers. Thus, the sequential polymerization is possible only when the first monomer is not a stronger nucleophile than the second monomer. 

In the random copolymerization process, both types of active species should be able to participate in the cross-propagation reactions. This imposes certain limitations on the choice of comonomers in the cationic polymerization of heterocyclic monomers. Onium ions, being the active species of these polymerizations, differ considerably in reactivity thus, as already discussed, oxonium ions initiate the polymerization of cyclic amines, whereas ammonium ions do not initiate the polymerization of cyclic ethers and the corresponding cross-propagation reaction would not proceed ... 

Cyclic ethers are oxidized to lactones in the presence of cerium(IV) salts. Treatment of tetrahydiofu-ran with cerium(rV) ammonium nitrate in the presence of primary, secondary or tertiary alcdiols leads to the formation of the corresponding tetrahydrofuranyl ethers in quantitative yield. Fuitfaermoie, 4-meth-oxybenzyl ether derivatives of carbohytbates are selectively deprotected to the parent alcohols on reaction with cerium(IV) ammonium nitrate in aqueous acetonitrile. ... 

The other onium salts (sulfonium or ammonium salts) are less often applied due to their lower reactivity. They can neither initiate the polymerization of cyclic ethers or acetals nor be displaced by less nucleophilic ligands (cyclic sulfides and amines respectively). 

The rigid binaphthyl units occupy planes that are perpendicular to the plane of the cyclic ether. One of the naphthalene rings forms a wall that extends along the sides and outward from the other face of the cyclic ether. The substituents attached at the 3-position of the naphthalene rings extend along the side or over the face of the cyclic ether. In the presence of a chiral primary amine, it forms a triple hydrogen bond with the primary ammonium cation. The same complex is formed whether the guest approaches from the top or from the bottom of the crown ether, as the crown ether... 

Treatment of cyclopropyl sulfides bearing a hydroxy group in the side chain with ceric ammonium nitrate (CAN) in methanol gives five- and six-membered cyclic ethers.In this reaction, the formation of cyclic ethers is understood by assuming a single electron transfer mechanism, which involves ring opening of the cation intermediate followed by intramolecular nucleophilic addition. 

Tetrahydropyranyl ethers. Alcohols in refluxing tetrahydropyran not dihydropyran) form THP ethers in the presence of the ammonium persulfate (9 examples, 86-95%). Oxidation of the cyclic ether precipitates the reaction. 

In the same way, they dismiss the hypothesis of a quaternary anunonium salt resulting from the reaction of the base with the oxide, since aromatic amines do not react with cyclic ethers. On the other hand, they observed the formation of an ammonium salt accumulating in the system ... 

Phase-transfer catalysts e.g. benzyltriethylammonium chloride and tetrabutyl-ammonium bromide) have been used in the preparation of O-methyl and 0-benzyl ethers and acetals of formaldehyde e.g. methyl 4,6-O-benzylidene-2,3-0-methylene-a-D-mannopyranoside). A new cyclic ether, methyl 4,6-0-benzylidene-2,3-0-ethylene-a-D-glucopyranoside, resulted when methyl 4,6-0-benzylidene-a-D-glucopyranoside reacted with 1,2-dichloroethane under basic aqueous conditions in the presence of a phase-transfer catalyst. Partially protected sugars e.g. l,2 5,6-di-0-isopropylidene-a-D-gIucofuranose) have also been methylated and benzylated by reaction with methyl and benzyl trifluoro-methanesulphonate (triflate), respectively, using 2,6-di-t-butylpyridine as base. The reactions with benzyl triflate, prepared in situ from benzyl alcohol and trifluoromethanesulphonic anhydride, occurred readily at ca. — 70 °C, whereas those with methyl triflate were performed in refluxing dichloromethane. 

The data bank presently holds records for the following classes of substances alkanes, cycloalkanes, chain and cyclic ethers, alcohols, chain and cyclic esters (lactones), chain and cyllc amides (lactams), amines and ammonium ions, saccharides, coordination complexes, chloroalkanes. More classes and more substances are being added as optimisation progresses. 

In the case of the bases derived from quaternary heterocyclic ammonium salts, the carbinolamines (5) can react as cyclic aldehyde-ammonias with many reagents with which the amino-aldehyde (7) could react. However, reactions of the carbinolamines which are not characteristic of amino-aldehydes are also known. Carbinolamines can easily be reconverted into the quaternary salts by the action of dilute acids, and they form alkyl ethers very easily with alcohols. If these last reactions do not occur, then this is convincing evidence for the base possessing the amino-aldehyde structure. However, if these reactions do occur this does not provide unambiguous confirmation of the carbinolamine structure. They are also given by the bi-molecular ethers (8), and, in the case of a tautomeric equilibrium... 

Nitration of the potassium enolates of cycloalkanones with pentyl nitrate81 or nitration of silyl enol ethers with nitronium tetrafluoroborate82 provides a method for the preparation of cyclic a-nitro ketones. Trifluoroacetyl nitrate generated from trifluoroacetic anhydride and ammonium nitrate is a mild and effective nitrating reagent for enol acetates (Eq. 2.41).83... 

Silica gel-based catalytic systems have been described as efficient promoters for a number of organic reactions.28 Illustrative examples include the oxidative cleavage of double bonds catalyzed by silica-supported KM11O4,29 reaction of epoxides with lithium halides to give /i-halohydrins performed on silica gel,30 selective deprotection of terf-butyldimethylsilyl ethers catalyzed by silica gel-supported phosphomolybdic acid (PMA),31 and synthesis of cyclic carbonates from epoxides and carbon dioxide over silica-supported quaternary ammonium salts.32... 

For example, the reaction of nitronates (123) with a zinc copper pair in ethanol followed by treatment of the intermediate with aqueous ammonium chloride a to give an equilibrium mixture of ketoximes (124) and their cyclic esters 125. Heating of this mixture b affords pyocoles (126). Successive treatment of nitronates (123) with boron trifluoride etherate and water c affords 1,4-diketones (127). Catalytic hydrogenation of acyl nitronates (123) over platinum dioxide d or 5% rhodium on aluminum oxide e gives a-hydroxypyrrolidines (128) or pyrrolidines 129, respectively. Finally, smooth dehydration of a-hydroxypyrrolidines (128) into pyrrolines (130f) can be performed. 

Use of TMSCl in combination with HMPA, DMAP, or TMEDA all favored 1,2-addition over 1,4-addition. Sequential a-alkoxyalkylcuprate conjugate addition, enolate trapping with TMSCl, and silyl enol ether alkylation provides a one-pot synthesis of tetrahydrofurans (Scheme 3.35) [129]. Cyclic enones afford as-fused tetrahydrofurans, while acyclic systems give complex mixtures of diastereomers. a-Alkoxyalkylcopper reagents also participate in allylic substitution reactions with ammonium salts [127]. 

The reaction of hexamine dinitrate (241) with 98% nitric acid at —30°C, followed by quenching with aqueous sodium nitrate, yields the nitrosamine (244). When the same reaction is cautiously quenched with ethanol the ethoxyether (245) is obtained. Treatment of the ethoxyether (245) with cold absolute nitric acid yields the bicyclic ether (246). ° Treatment of any of the cyclic nitramines (242)-(246) with nitric acid and ammonium nitrate in acetic anhydride yields RDX. ° Hexamine dinitrate is often used in low temperature nitrolysis experiments in order to avoid the initial exotherm observed on addition of hexamine to nitric acid. 

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