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18-crown preparations

Impressions of inlay and crown preparations, and all gingival areas, are best obtained by filling the preparation or gingival area with impression material injected from a hypodermic syringe. This eliminates trapping air in the corners and recesses and gives a more faithful reproduction without nodules or other imperfections. [Pg.491]

Hyde, Shaw and Shepherd, apparently unaware of the bis-crowns prepared by Smid et reported a similar compound but by a remarkable route. In a survey... [Pg.36]

Intrinsic reactivity, gas-phase study applications, 1, 803 Inverse crowns, preparation and reactions, 2, 109 Involatile liquids, in metal vapor synthesis, 1, 229 Involatile solids, in metal vapor synthesis, 1, 229 Iodide ligands... [Pg.128]

Reactions such as the one that gave Pedersen the first crown can produce additional products. Thus, catechol (1,2-dihydroxybenzene) reacts with 0(CH2CH2)2C1 in the presence of base to give dibenzo-18-crown-6. Tribenzo-27-crown-9 and benzo-9-crown-3 have also been identified as resulting from this process. For this reason, such crown preparations are sometimes referred to as shotgun reactions. Attempts have been made to direct the cyclization to the correct receptor size by including a K+ template ion to direct formation of 18-membered ring. [Pg.807]

Simplest examples are prepared by the cyclic oligomerization of ethylene oxide. They act as complexing agents which solubilize alkali metal ions in non-polar solvents, complex alkaline earth cations, transition metal cations and ammonium cations, e.g. 12—crown —4 is specific for the lithium cation. Used in phase-transfer chemistry. ... [Pg.116]

Aryl, heteroaryl, and alkenyl cyanides are prepared by the reaction of halides[656-658] or triflates[659,660] with KCN or LiCN in DMF, HMPA, and THF. Addition of crown ethers[661] and alumina[662] promotes efficient aryl and alkenyl cyanation. lodobenzene is converted into benzonitrile (794) by the reaction of trimethylsiiyl cyanide in EtiN as a solvent. No reaction takes place with aryl bromides and chlorides[663]. The reaction was employed in an estradiol synthesis. The 3-hydroxy group in 796 was derived from the iodide 795 by converting it into a cyano group[664]. [Pg.246]

The strength of this bonding depends on the kind of ether Simple ethers form relatively weak complexes with metal ions but Charles J Pedersen of Du Pont discovered that cer tain polyethers form much more stable complexes with metal ions than do simple ethers Pedersen prepared a series of macrocyclic polyethers cyclic compounds contain mg four or more oxygens m a ring of 12 or more atoms He called these compounds crown ethers, because their molecular models resemble crowns Systematic nomencla ture of crown ethers is somewhat cumbersome and so Pedersen devised a shorthand description whereby the word crown is preceded by the total number of atoms m the ring and is followed by the number of oxygen atoms... [Pg.669]

In media such as water and alcohols fluoride ion is strongly solvated by hydro gen bonding and is neither very basic nor very nucleophilic On the other hand the poorly solvated or naked fluoride 10ns that are present when potassium fluoride dis solves m benzene m the presence of a crown ether are better able to express their anionic reactivity Thus alkyl halides react with potassium fluoride m benzene containing 18 crown 6 thereby providing a method for the preparation of otherwise difficultly acces sible alkyl fluorides... [Pg.671]

Inclusions of Other Grown Analogues. A variety of crown analogues and hybrid modifications (24—28) with other topological features (lariat ethers (31,32), octopus molecules (33), spherands (eg, (12) (34), torands (35)) including chiral derivatives (36) have been prepared and demonstrated to show particular inclusion properties such as chiroselective inclusion (Fig. 4) (37) or formation of extremely stable complexes (K ">(LR) for (12)... [Pg.62]

The unsaturation present at the end of the polyether chain acts as a chain terminator ia the polyurethane reaction and reduces some of the desired physical properties. Much work has been done ia iadustry to reduce unsaturation while continuing to use the same reactors and hoi ding down the cost. In a study (102) usiag 18-crown-6 ether with potassium hydroxide to polymerise PO, a rate enhancement of approximately 10 was found at 110°C and slightly higher at lower temperature. The activation energy for this process was found to be 65 kj/mol (mol ratio, r = 1.5 crown ether/KOH) compared to 78 kj/mol for the KOH-catalysed polymerisation of PO. It was also feasible to prepare a PPO with 10, 000 having narrow distribution at 40°C with added crown ether (r = 1.5) (103). The polymerisation rate under these conditions is about the same as that without crown ether at 80°C. [Pg.352]

Cesium isotopes can be recovered from fission products by digestion in nitric acid, and after filtration of waste the radioactive cesium phosphotungstate is precipitated using phosphotungstic acid. This technique can be used to prepare radioactive cesium metal or compounds. Various processes for removal of Cs isotopes from radioactive waste have been developed including solvent extraction using macrocycHc polyethers (62) or crown ethers (63) and coprecipitation with sodium tetraphenylboron (64). [Pg.379]

Chelation itself is sometimes useful in directing the course of synthesis. This is called the template effect (37). The presence of a suitable metal ion facihtates the preparation of the crown ethers, porphyrins, and similar heteroatom macrocycHc compounds. Coordination of the heteroatoms about the metal orients the end groups of the reactants for ring closure. The product is the chelate from which the metal may be removed by a suitable method. In other catalytic effects, reactive centers may be brought into close proximity, charge or bond strain effects may be created, or electron transfers may be made possible. [Pg.393]

Today, stainless steels find their primary use in wrought form for temporary appHcations such as orthodontic wires, brackets, and temporary crowns. The temporary crowns are obtained in preformed sizes/shapes and then are trimmed by the dentist with shears to fit over prepared teeth that are awaiting the fabrication of permanent cast crowns. [Pg.486]

Halide ions may attack 5-substituted thiiranium ions at three sites the sulfur atom (Section 5.06.3.4.5), a ring carbon atom or an 5-alkyl carbon atom. In the highly sterically hindered salt (46) attack occurs only on sulfur (Scheme 62) or the S-methyl group (Scheme 89). The demethylation of (46) by bromide and chloride ion is the only example of attack on the carbon atom of the sulfur substituent in any thiiranium salt (78CC630). Iodide and fluoride ion (the latter in the presence of a crown ether) prefer to attack the sulfur atom of (46). cis-l-Methyl-2,3-di-t-butylthiiranium fluorosulfonate, despite being somewhat hindered, nevertheless is attacked at a ring carbon atom by chloride and bromide ions. The trans isomer could not be prepared its behavior to nucleophiles is therefore unknown (74JA3146). [Pg.162]

Rate differences observed between the same bromophenylcarbene (241) when prepared by two different routes, diazirine photolysis and the reaction of benzylidene dibromide with potassium r-butoxide, vanish when a crown ether is added to the basic solution in the latter experiment. In this case the complexing potassium bromide is taken over by the crown ether, and selectivity towards alkenes reaches the values of the photolytic runs (74JA5632). [Pg.227]

Various materials are used in dental prosthetic practice for the preparation of dental implants, crowns, and bridges. Some of these materials contain copper, which is added in order to improve mechanical or/and chemical properties, but some of them may contain the copper as an impurity. Considering the fact that dental implants remain in the oral cavity for a long time, and that they are exposed to the corrosive action of oral fluids and various kinds of food and beverages, it is necessary to check their possible harmful effects upon the human health. [Pg.373]

This derivative has been prepared from an indole, the chloromethyl ether, and potassium hydride in 50% yield it is cleaved in 84% yield by potassium cyanide/ 18-crown-6 in refluxing acetonitrile/ ... [Pg.393]

Dibenzyl-14-crown-4 (lithium ionophore VI 6,6-dibenzyl-l,4,8,ll-tetra-oxa-cyclo-tetradecane) [106868-21-7] M 384.5, m 102-103°. Dissolve in CHCI3, wash with saturated aqueous NaCl, dry with MgSOa, evaporate and purify by chromatography on silica gel and gradient elution with C6Hg-MeOH followed by preparative reverse phase HPLC on an octadecyl silanised silica (ODS) column and eluting with MeOH. It can be crystd from MeOH (v Br 120 cm , C-O-C). [7 Chem Soc Perkin Trans 1 1945 1986.]... [Pg.417]

Sodium ionophore VI bis[(12-crown-4)methyl]dodecyl methyl malonate [80403-59-4] M 662.9. Purified by gel permeation or column chromatography. [Preparation and NMR data J Electroanal Chem 132 99 1982.]... [Pg.473]

Caution Crown ethers may be toxic. Due care should be exercised in the preparation and handling of l8-croum-6. An explosion has been reported... [Pg.30]

Extensive and important as Pedersen s efforts were, they might have been even greater had he not prepared the first examples of crown ethers when he was beyond sixty years of age. After giving birth to a remarkable child, he was unable to nurture it because of his retirement in 1969. [Pg.2]

The crown esters are actually macrocyclic lactones, the bulk of which rings are ethyl-eneoxy units. By far, the largest number of such compounds have been prepared by Bradshaw and his co-workers. Representative examples of such compounds are shown below. The name crab ethers has occasionally been applied to such structures, but as with the aquatic species noted above, this name has not found wide acceptance. [Pg.6]

Both of these structures are open-chained compounds corresponding to crown ethers in function if not exactly in structure (see Chap. 7). They have repeating ethyleneoxy side-chains generally terminated in a methyl group. Montanari and co-workers introduced the polypodes 22 as phase transfer catalysts . These compounds were based on the triazine nucleus as illustrated below. The first octopus molecule (23) was prepared by Vogtle and Weber and is shown below. The implication of the name is that the compound is multiarmed and not specifically that it has eight such side-chains. Related molecules have recently been prepared by Hyatt and the name octopus adopted. For further information on this group of compounds and for examples of structures, refer to the discussion and tables in Chap. 7. [Pg.7]

The template effect has long been accepted prima facie by workers in the crown field because of the obvious relationship between ring size and complexation constant. In fact, Cram stated in 1975 that the templating properties of for preparing crown ethers is well established.. . In fact, the template effect was widely acknowledged and has always received overwhelming support. Nevertheless, few direct comparisons are available in the literature and we have restricted ourselves m this discussion only to direct rather than the large body of presumptive evidence which is currently available. [Pg.18]

Over the years, 18-crown-6 has probably been utilized in more applications than any other erown with the possible exception of dibenzo-18-crown-6. There are several reasons for this. First, simple syntheses of 18-crown-6 have been available for a long time and the molecule may be prepared from very inexpensive starting materials. Equally important, however, is the fact that 18-crown-6 is a very strong binder for a number of alkali metals, especially sodium and potassium cations. [Pg.21]

Two of the most widely used crown ethers have been dibenzo-18-crown-6 and dicyclo-hexano-18-crown-6.(In older literature, the latter is often referred to as dicyclohexyl-18-crown-6 .) A major reason for this is that Pedersen reported complete details of the preparation of both compounds in Organic Syntheses in 1972. As a result, both compounds were readily prepared and available. [Pg.23]

Pedersen s preparation of dibenzo-18-crown-6 involves catechol and bis(2-chloroethyl) ether. In this procedure, sodium hydroxide is used as base and M-butanol as solvent. The reactants are heated overnight and the crude crown is obtained by precipitation from acetone in which it is almost completely insoluble. The yield range specified is 39—48% and is readily realized. The overall preparation is illustrated in Eq. (3.11). [Pg.23]


See other pages where 18-crown preparations is mentioned: [Pg.250]    [Pg.159]    [Pg.190]    [Pg.177]    [Pg.187]    [Pg.210]    [Pg.326]    [Pg.72]    [Pg.474]    [Pg.490]    [Pg.467]    [Pg.31]    [Pg.32]    [Pg.1]    [Pg.1]    [Pg.2]    [Pg.4]    [Pg.12]    [Pg.15]    [Pg.16]    [Pg.22]   
See also in sourсe #XX -- [ Pg.11 ]




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