10501-16-3

Upstream product

• 67-56-1 methanol 
• 7314-85-4 2-adamantyl bromide 
• 18971-91-0 2-iodoadamantane 
• 768-90-1 1-Adamantyl bromide 
• 41736-95-2 spiro[adamantane-2,3'-diazirine] 
• 128337-02-0 2-(phenylthio)tricyclo<3.3.1.1^3,7>decane 
• 39257-31-3 1,2-di-iodoadamantane 

Downstream Products

• 19213-98-0 4^e-Brom-2-tricyclo<3.3.1.1^3,7>decanon 

Relevant academic research and scientific papers

Chemospecific monofunctionalization of α-cyclodextrin in the solid state

(matrix presented) The properties of the self-assembling aziadamantane inclusion complex with two α-cyclodextrin molecules have been exploited to perform a chemospecific monofunctionalization of α-cyclodextrin. The insertion of the photochemically generated carbenes takes place chemospecifically into the cyclodextrin's C-3-OH and C-2-OH bonds in 39 and 18% yield, respectively. This model reaction surpasses conventional methods in terms of yield as well as selectivity.

More on adamantene

At high dilution and temperature adamantene undergoes a retro Diels - Alder cycloaddition to a triene, as well as retro-insertion reactions to give carbenes. 1,2-Diiodoadamantane and 3-diiodomethylnoradamantane react with methyllithium in the gas phase to give adamantene, which is efficiently reduced to adamantane under these conditions. Addition of adamantene to butadiene occurs in 4 + 2 and 2 + 2 fashion.

Photoelimination of nitrogen from adamantane and pentacycloundecane (PCU) diazirines: A spectroscopic study and supramolecular control

Photochemical reactivity of pentacycloundecane (PCU) and adamantane diazirines was investigated by preparative irradiation in different solvents, laser flash photolysis (LFP) and quantum chemical computations. In addition, formation of inclusion complexes for diazirines with cucurbit[7]uril, β- and γ-cyclodextrin (β- and γ-CD) was investigated by 1H NMR spectroscopy, isothermal microcalorimetry and circular dichroism spectroscopy, followed by the investigation of photochemical reactivity of the formed complexes. Diazirines undergo efficient photochemical elimination of nitrogen (ΦR > 0.5) and deliver the corresponding singlet carbenes. Singlet carbenes react in intra- and intermolecular reactions and we found a rare singlet carbene pathway in CH3OH involving protonation and formation of a carbocation, detected due to the specific rearrangement of the pentacycloundecane skeleton. Singlet diazirines undergo intersystem crossing and deliver triplet carbenes that react with oxygen to form ketones which were isolated after irradiation. Our main finding is that the formation of diazirine inclusion complexes with β-CD and γ-CD changes the relative ratio of singlet vs. triplet pathways, with singlet carbene products being dominant from the chemistry of the irradiated complexes. Our combined theoretical and experimental studies provide new insights into the supramolecular control of carbene reactivity which has possible applications for the control of product distribution by solvent effects and the choice of constrained media.

Carbenes in constrained systems. 2. First carbene reactions within zeolites - Solid state photolysis of adamantane-2-spiro-3′-diazirine

Inclusion complexes of adamantane-2-spiro-3′-diazirine (1) in different X- and Y-type zeolites (faujasite) have been prepared. These complexes were analyzed by FT-IR and 13C CP-MAS NMR spectroscopy. The guest-host complexes were irradiated with UV light in the solid state and the reaction products separated from the host and analyzed. Product ratios obtained in zeolites are totally different from those obtained by irradiation of 1 in solution or as a pure compound. In zeolites the main products isolated are 2,4-dehydroadamantane (4) and 2-adamantanol (6). In addition, adamantanone (5) and adamantane are formed. While 2-adamantanol (6) is thought to be a product from an acid-catalyzed reaction, the strained 2,4-dehydroadamantane (4) derives from an intramolecular 1,3 C-H insertion of adamantanylidene (3). In stark contrast to reactions in solution, in zeolites the formation of adamantanone azine (7) resulting from an intermolecular reaction is only of minor significance.

Photochemistry of phenyl thioethers and phenyl selenoethers. Radical vs ionic behavior

In analogy with alkyl iodides and bromides, the phenyt thio- and selenoethers 2a,b, 13a, 21b,c and 35 displayed competing radical and ionic photobehavior on irradiation in solution, via a mechanism thought to involve initial homolytic cleavage of the alkyl C-S or C-Se bond followed by electron transfer within the resulting radical pair cage (Scheme I). These are the first examples of ionic photobehavior to be recognized for the C-SAr and C-SeAr chromophores. The electronegatively substituted pentafiuorophenyl analogues 2c, 13b, and 21d displayed enhanced ionic photobehavior. By contrast, the 4-methoxyphenyl derivative 21a exhibited almost exclusively radical behavior. The sulfoxide (2R*,R*s)-21f displayed principally radical behavior, accompanied by epimerization at sulfur. The quantum yields for the disappearance of the 2-norbornyl ethers 21b and 21c were 0.53-0.64 in solution and rose to 0.89-0.95 in the presence of suspended fumed silica. Irradiation of the phenyl thioether 21b on silica gel resulted in nucleophilic trapping by surface silanol groups to afford covalently bound material (33), which afforded chloride 34 on treatment with SOCl2. Irradiation of phenyl thioethers 2a and 35, phenyl selenoether 2b, or C6H5SH in allyl alcohol solution afforded acetal 11, apparently via isomerization of some of the solvent to propanal (44) followed by acetalization. Irradiation of alcoholic solutions of aldehydes containing C6H5SH is a useful means of generating acetals under neutral conditions.

Photochemistry of alkyl halides. 12. Bromides vs Iodides

Conditions have been developed for optimizing ionic photobehavior material balances from alkyl bromides. Hydroxide ion as an efficient for the byproduct HBr while giving minimal competing photoreduction via electron transfer to the alkyl bomide. The photobehavior of bromides 1, 11, 25, and 40 has examined and with that of the corresponding iodides 2, 12, 26, 41 under conditions. In each case, the bromide higher yields of products derived from out of cage radical intermidiates than the corresponding iodide. However, with the 2-norbornyl bromides 11 and iodides 12 showed that, of products not formed from the out of cage 2-norbornyl radical 13, the bromides 11 gave a higher percentage of products from the ionic intermediates 15 and 16 than did the iodides. Thus, electron transfer within the radical pair 14 is apparently more rapid for bromides than iodides, as expected on the of the relative electronegativities of bromine iodine. It is that the substantially higher yields of out of radical products from alkyl bromides may be due in to formation of the radical pair with greater excess energy, which results in more rapid escape from the cage. The epimeric 2-norbornyl bromides 11x and 11n underwent no detectable interconversion and afforded somewhat different product ratios. The more hindered epimer 11n underwent conversion to products at a slower than 11x. By contrast, 12x and 12n underwent substantial interconversion via out of transfer of an iodine atom from iodide 12 to radical 13. Epimerization was significantly attenuated in the more viscous solvent tert-butyl alcohol.

REACTION OF 1-BROMOADAMANTANE WITH AN ALCOHOL SOLUTION OF ALKALI

The main direction in the reaction of 1-bromotricyclo3,7>decane with an alcohol solution of potassium hydroxide is solvolysis with the formation of tricyclo3,7>decan-1-ol and tricyclo3,8>decan-3-ol.Dehydrobromination takes place to a lesser degree, leading to tetracyclo3,7.02,4>decane and tricyclo3,8>dec-4-ene.