Tricyclo decane, adamantane

The calculation of the vibrational properties of hydrocarbons using density functional theory is usually in very good agreement with the INS experimental spectra. The treatment of the data has to take into consideration not only the contribution of the fundamentals but also the combinations and overtones. The effect of the lattice vibrations is included in an ad hoc manner ( 5.3). As an example of the usefulness of the isolated molecule approach, in Fig. 4.6 we show the experimental and calculated spectra of adamantane (tricyclo[3.3.l.l ]decane, CjoHie). 

More polycyclic alkanes have been treated by INS spectroscopy. The spectrum of of adamantane (tricyclo[3.3.1.1 ]decane, CioHie) is shown in Fig. 4.6. Norbomane and some of its mono- and dimethyl derivatives (see Fig. 8.5 for the structures) were extensively studied and force fields developed using the Wilson GF matrix method [17—19]. Given the low symmetry and relatively large number of atoms present, this was a tour de force of spectroscopy. 

Let us describe some frequently encountered polycyclic structures. Bicyclo[2.2.1] heptane, also known as norbomane, is the basic structure of a series of natural products. The tricyclic compound adamantane (tricyclo[3.3.1.L ]decane) is in principle the smallest structural fragment of diamond and its structure appears on the list of pharmaceutically important products. Adamantane was synthesized for the first time in 1941 at the University of Zagreb by Vladimir Prelog. 

Adamantane, tricyclo[3.3.1.1]decane [281-23-2] (14), can be produced by heating tetrahydrodicyclopentadiene [6004-38-2] (15) in the presence of aluminum trichloride (79). It is the base for drugs that control German measles and influenza (79,80). 

The details of the process shown in this footnote are not known. However, it is possible that partial hydrolysis of the adamantane (tricyclo[3.3.1.E ]decane, Chapter 1) analogue hexamethylenetetramine (l,2,5,8-tetraazatricyclo[3.3.1.1 - ]decane) to formaldehyde (methanal, CH2O) and ammonia (NH3), from which it was formed by a condensation reaetion (see Chapter 10), provides an oxidizing agent (methanal). 

Adamantane (CAS No 281-23-2) l-tricyclo[3.3.1.1 ]decane is a cage hydrocarbon with a white or almost white crystalline solid nature, like solid wax, at normal conditions. Its odor resembles that of camphor. It is a stable and nonbiodegradable compound that is combustible due to its hydrocarbon nature. It has not been found to be hazardous or toxic to living entities [14, 15]. It should be pointed out that adamantane can exist in gas, liquid, and two solid crystalline states. 

Wiseman and coworkers have succeeded in preparing tricyclo[5.3.0.0 ]decane (393), a CioHig hydrocarbon which unlike adamantane is chiral. Their elegantly simple approach entails Diels-Alder addition of cyclobutene to l,4-dihalocyclohexa-l,3-dienes, catalytic hydrogenation of the adduct, reaction with aluminium triiodide, and ultimately di- -butyltin dihydride reduction. 

A mixture of 0.27 mtnol of tricyclo[3.3.1.1 3,7]decane (adamantane), 0.054 mmol of (Bu4N)4Wl()032, and 3 mg of platinum in 10 mL of acetonitrile under argon in a Pyrex Schlenk flask is irradiated with a 550 W mercury arc lamp. The reaction turns deep blue on photolysis. Every 16 h, photolysis is Stopped, the catalyst is reoxidized under air, the sample is degassed and again placed under an argon atmosphere, and irradiation is resumed. After a total of 64 h there is 58% conversion of adamantane and a 40% yield of the methyl ketone (by VPC). 

To a stirred solution of [4-(2-pyrimidinyl)piperazino]ethylamine (2.0 g, 0.01 mol) in 50 ml of methylene chloride, adamantane-l-carboxylic acid chloride (3.6 g, 0.018 mol) and triethylamine (2.9 g, 0.015 mol) were added. Stirring was continued at room temperature overnight. The methylene chloride solution was washed with water, dried over anhydrous sodium sulfate and evaporated under reduced pressure. The remaining residue was subjected to preparative HPLC. The residue was dissolved in ethyl acetate (10 ml) and subjected to flash chromatography using a 9 inch column of silica gel and ethyl acetate as the eluent. The N-[2-[4-(2-pyrimidinyl)-l-piperazinyl]ethyl]tricyclo[3.3.1.1(3,7)] decane-l-carboxamide was separated. 

Adamantane, 2-azido-2-phenyl- (8) Tricyclo[3.3.1.13,7]decane, 2-azido-2-phenyl- (9) (65218-96-4)... 

SYNS ADAMANTANAMINE HYDROCHLORIDE ADAMANTINE HYDROCHLORIDE ADAMANTYL-AMINE HYDROCHLORIDE 1-ADAMANTYL-AMINE HYDROCHLORIDE AMANTADINE HYDROCHLORIDE AMAZOLON AMINO-ADAMANTANE HYDROCHLORIDE 1-AMNO-ADAMANTENE HYDROCHLORIDE EXP 105-1 MANTADAN NSC-83653 SYMMETREL TRICYCLO(3.3.1.1.07))DECAN-1-AMINE, HYDROCHLORIDE (9CI) VIROFRAL... 

For each type of assay, the label or tag involved is listed along with typical substrates, type of absorbance, and type of instrument required. RIA radioimmunoassay IRMA immunoradiometric assay CPM counts per minute ELISA enzyme linked immunosorbent assay EIA enzyme immunoassay TMB 5,5 tetramethylbenzidine HPA p hydroxyphenylacetic acid AMPPD 4 methoxy 4 (3 phosphatephenyl) spiro(l,2 dioxetane) 3,2 adamantane p NPP p nitrophenyl phosphate 4 MUP 4 methylumbelliferyl phosphate ONPG o nitrophenyl P galactopyranoside MUG 4 methylumbelliferyl P D galactopyrano side AMPGD 3 (4 methoxyspiro( 1,2 dioxetane 3,2 tricyclo(3.3.1.1(3,7))decan) 4 yl)phenylgalacto pyranoside ECL electrochemiluminescence. 

Brossi, M., and C. Ganter. 1988. The adamantane rearrangement of syn- and anti-tricyclo[4.2.1.12,5]decane. Part II. Rearrangements initiated by regioselective formation of carbocations at C(3) and C(9). Helv. Chim. Acta 71 848. 

On the other hand, R-exchanged zeolites have also been used in combination with a metal function, for carrying out the isomerization and hydrocracking of paraffins and cycloalkanes. This is the case for isomerization of n-hexane to isohexane and 2,2-dimethyl-butane (Rabo et al. 1961) the isomerization of n-undecane to mixed Ci 1 isomers at 275°C on Pt/Ce-Y zeolite (Weitkamp et al. 1985) the isomerization of c (7o-exo-tricyclo[5.2.1.02,6]-decane or exo-tricyclo[6.2.1.02,7]-undecane into adamantane or 1-methyladamantane, respectively, on R-Y at 150-270°C (Lau and Maier 1987) the isomerization of tetrahydrodicyclopentadiene into adamantane on Re-Y in a H2/HC1 atmosphere at 250°C (Honna et al. 1986) or the double bond relocation of 2-alkyl acrolein into fran.j-2-methyl-2-alkenals over Ce,B-ZSM-5 (Fisher et al. 1986). Recently, it has been reported that Ce-promoted Pd/ZSM-5 is an active and selective catalyst in the dehydroisomerization of a-limonene to / -cymene (Weyrich et al. 1997). 

For tricyclo[4.3.1.0 ]decane the following trivial names were introduced in the literature isoadamantane (1968) protoadamantane (1968) isotwistane (1969) and 2(3 - 4)abeo-adamantane (1970) In the present review the name isotwistane will be applied, which until now is exclusively used to describe such 2,7-dihetero-tricyclodecanes. However, one should pay attention to the fact that since 1972 the trivial name iso-twistane is also applied for tricyclo[4.3.1.0 )decanes. 

The Lewis-acid-catalysed rearrangement of polycyclic hydrocarbons C H2 4 c (x = 1,2,3,...) into their thermodynamically more stable diamond-like isomers is usually referred to as the adamantane rearrangement . The archetype of this unique isomerization is the AlCl3-catalyzed transformation of en /o-tricyclo[5.2.1.0 ]decane (11) (tetrahydrodicyclopentadiene) into adamantane (Ad-H) (Scheme 4), which was first discovered by Schleyer " more than 30 years ago. This process is thermodynamically controlled and it involves carbenium ion intermediates which rearrange via successive 1,2-C bond and 1,3 hydride shifts. Numerous theoretical and experimental investigations have established the most direct thermodynamically feasible pathway (exo-11 -> 12 13 -> 14 -> 15 Ad-H) for the isomerization of endo-11 to adamantane. 

SCHEME 4. The most direct pathways in the adamantane rearrangement of tricyclo[5.2.1.0 ]decane (11)... 

Of the many important superacid-catalyzed isomeriza-tions, the isomerization tricyclo [5.2.1.0 ] decane to adamantane is unique, a reaction discovered by Schleyer. 

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