2- adamantane

Submitted by Paul von R. Schlever, M. M. Donaldson, R. D. Nicholas, and C. Cdpas.  

When the removal of the ether is complete, the condenser at the top of the column is replaced by a wide-diameter adapter the bottom of which is placed in a receiver flask immersed in an ice bath. The adapter is heated (Note 2) to prevent premature solidification of the distillate. The distillation is continued and the e o-tetrahydrodicyclopentadiene, b.p. 191-193°, is collected. 

The yield is 196-200 g. (96.5-98.4%). The melting point depends on the purity of the starting material but generally is above 65°. 

Technical grade dicyclopentadiene is purified by distillation at water pump pressure through a 30-cm. Vigreux column, and 

The adapter can readily be heated by placing an infrared lamp above it. 

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Figure 2-34. Reduction of a substituted adamantane and phenylalanine to ring skeletons by pruning acyclic parts of the molecules.

Figure 2-36. Identification of the number of rings in adamantane after graph reduction (the different ring systems are highlighted with bold lines). Note that a graph does not car 3D information thus, the two structures on the upper right-hand side are identical.

Chiral carbon atoms are common, but they are not the only possible centers of chirality. Other possible chiral tetravalent atoms are Si, Ge, Sn, N, S, and P, while potential trivalent chiral atoms, in which non-bonding electrons occupy the position of the fourth ligand, are N, P, As, Sb, S, Se, and Te. Furthermore, a center of chirality does not even have to be an atom, as shown in the structure represented in Figure 2-70b, where the center of chirality is at the center of the achiral skeleton of adamantane. 

Find the MM3 enthalpy of formation of 1- and 2-methyladamantane. Use the Rings tool and the adamant option to obtain the base structure of adamantane itself. Use the Build tool to add the methyl group. 1-Adamantane is the more symmetrical structure of the two isomers. 

Protonation of formic acid similarly leads, after the formation at low temperature of the parent carboxonium ion, to the formyl cation. The persistent formyl cation was observed by high-pressure NMR only recently (Horvath and Gladysz). An equilibrium with diprotonated carbon monoxide causing rapid exchange can be involved, which also explains the observed high reactivity of carbon monoxide in supera-cidic media. Not only aromatic but also saturated hydrocarbons (such as isoalkanes and adamantanes) can be readily formylated. 

Although it is not a reaction of alkenes, oxidation of some alkanes with Pd(ll) is cited here. 1-Adamantyl Irilluoroacetate (155) was obtained in above 50% yield by the reaction of adamantane with Pd(OAc)2 in trifluoroa-cetic acid at 80 C[171]. 

Acyl peroxides Acyl thiophenes Adalat Adamantane Adamantane [281-23-2]... 

Chiral separations are concerned with separating molecules that can exist as nonsupetimposable mirror images. Examples of these types of molecules, called enantiomers or optical isomers are illustrated in Figure 1. Although chirahty is often associated with compounds containing a tetrahedral carbon with four different substituents, other atoms, such as phosphoms or sulfur, may also be chiral. In addition, molecules containing a center of asymmetry, such as hexahehcene, tetrasubstituted adamantanes, and substituted aHenes or molecules with hindered rotation, such as some 2,2 disubstituted binaphthyls, may also be chiral. Compounds exhibiting a center of asymmetry are called atropisomers. An extensive review of stereochemistry may be found under Pharmaceuticals, Chiral. 

Low temperature fluorination techniques (—78° C) are promising for the preparation of complex fluorinated molecules, especiaUy where functional groups are present (30), eg, fluorination of hexamethjiethane to perfluorohexamethylethane [39902-62-0] of norbomane to perfluoro- (CyF 2) 1-hydro undecafluoronorbomane [4934-61 -6] C HF, and of adamantane to 1-hydropentadecafluoroadamantane [54767-15-6]. 

Hexamethylenetetramine. Pure hexamethylenetetramine [100-97-0] (also called hexamine and HMTA) is a colorless, odorless, crystalline sohd of adamantane-like stmcture (141). It sublimes with decomposition at >200° C but does not melt. Its solubiUty in water varies Htde with temperature, and at 25°C it is 46.5% in the saturated solution. It is a weak monobase aqueous solutions are in the pH 8—8.5 range (142). Hexamethylenetetramine is readily prepared by treating aqueous formaldehyde with ammonia followed by evaporation and crystallisation of the soHd product. The reaction is fast and essentially quantitative (142). 

Hexamethylenetetramine. Hexa, a complex molecule with an adamantane-type stmcture, is prepared from formaldehyde and ammonia, and can be considered a latent source of formaldehyde. When used either as a catalyst or a curative, hexa contributes formaldehyde-residue-type units as well as benzylamines. Hexa [100-97-0] is an infusible powder that decomposes and sublimes above 275°C. It is highly soluble in water, up to ca 45 wt % with a small negative temperature solubiUty coefficient. The aqueous solutions are mildly alkaline at pH 8—8.5 and reasonably stable to reverse hydrolysis. 

The synthesis of adamantane (15), tricyclo[3.3.1.1 ]decane [281-23-2] by heating tetrahydrodicyclopentadiene (14) [6004-38-2] in the presence of aluminum trichloride illustrates another aspect of the synthetic utiHty of DCPD (80). Adamantane is the base for dmgs that control German measles and influenza (80-81) (see ANTIVIRAL AGENTS). 

In another experiment tritiated adamantane diazirine fixed to the hydrocarbon core of a membrane gave rise to carbene insertion into the catalytic subunit of ATP-ase. After protolytic degradation adjacent areas of the original structure became evident (80JBC(255)860). 

Adamantane acetic acid [4942-47-6] M 194.3, m 136 , pK jtDissolve in hot N NaOH, treat with charcoal, filter and acidify. Collect solid, wash with H2O, dry and recryst from MeOH. [Chem Ber 92 1629 1959.]... 

Perfluorodimethyladamantane is prepared from adamantane dicarboxylic acid by treatment with sulfur tetrafluoride followed by energetic fluorination with cobalt trifluoride over two temperature ranges [S] (equation 15)... 

Several reagents are compared in their ability to fluorinate adamantane [2 42, 43, 44, 45, 46 47, 48 (equation 22) Cyclohexane behaves in a similar fashion but gives lower yields [3, 42, 49 ... 

Xenon difluoride fluorinates adamantane in low yield [45] (equation 22) When the carbon-hydrogen bond is activated by an a-sulfur atom, fliiorination occurs readily The reactions involve intermediates that contain sulfur-fluorine bonds. At-Fluoropyridinium reagents behave similarly [99, 100, 101, 102] (equations 55-57)... 

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