815-24-7

Usage

Uses

Used in Chemical Synthesis:
Hexamethylacetone is used as a synthetic intermediate for the preparation of di-tert-butyladamantylcarbinol by reacting with 1-bromo-adamantane. This reaction is an important step in the synthesis of various organic compounds and pharmaceuticals.
Used in Pharmaceutical Industry:
Hexamethylacetone can be used as a starting material for the synthesis of various pharmaceutical compounds. Its unique structure and reactivity make it a valuable building block in the development of new drugs and therapeutic agents.
Used in Research and Development:
Hexamethylacetone is also used in research and development laboratories for the synthesis of novel compounds and the study of chemical reactions. Its versatility and reactivity make it a valuable tool for chemists and researchers working in various fields of chemistry.

Synthesis Reference(s)

Journal of the American Chemical Society, 71, p. 4141, 1949 DOI: 10.1021/ja01180a082The Journal of Organic Chemistry, 39, p. 611, 1974 DOI: 10.1021/jo00919a007

InChI:InChI=1/C9H18O/c1-8(2,3)7(10)9(4,5)6/h1-6H3

Upstream product

• 594-19-4 tert.-butyl lithium 
• 15719-64-9 methylammonium carbonate 
• 677-22-5 tert-butylmagnesium chloride 
• 3282-30-2 pivaloyl chloride 
• 565-80-0 2,4-dimethylpentan-3-one 
• 74-88-4 methyl iodide 
• 54396-69-9 Di-tert-butyl thioketone 
• 35895-37-5 2,4-dimethyl-3-iodopent-2-ene 
• 2259-30-5 tert-butylmagnesium bromide 
• 56583-96-1 tert-butylcopper(I) 
• 100330-57-2 3,3-Di-tert-butyl-4-methoxy-[1,2]dioxetane 
• 630-19-3 pivalaldehyde 
• 75-97-8 3,3-dimethyl-butan-2-one 
• 1026163-32-5 4-(1,1-dimethylethyl)-4-hydroxy-2,2,5,5-tetramethyl-3-hexyl N-(4-toluenesulfonyl)carbamate 

Downstream Products

• 5857-69-2 2,2,3,4,4-pentamethyl-3-pentanol 
• 32579-71-8 2,2,4,4-tetramethyl-3-neopentylpentan-3-ol 
• 4298-71-9 1-chloro-2,2,4,4-tetramethyl-pentan-3-one 
• 40544-06-7 4-Nitro-benzoic acid 1-tert-butyl-1-(4-chloro-phenyl)-2,2-dimethyl-propyl ester 
• 40544-05-6 Phenyl-di-t-butylcarbinol-p-nitrobenzoat 
• 20818-91-1 3-tert-butyl-2,2,5,5-tetramethyl-3-(4-nitro-benzoyloxy)-hexane 
• 37892-63-0 3-tert-butyl-4,4-dimethyl-1-phenylpent-1-yn-3-ol 
• 54440-13-0 2-(1,1-dimethylethyl)-3,3-dimethyl-1-phenylbut-1-ene 
• 3229-31-0 p-nitrophenyl-t-butylaminoxyl 
• 17226-40-3 3-(4'-methoxyphenyl)-2,2,4,4-tetramethylpentan-3-ol 
• 2048-07-9 1,2-bis(2-methylphenyl)-1,2-ethanedione 
• 118712-16-6 3-(2,4-Dimethyl-phenyl)-2,2,4,4-tetramethyl-pentan-3-ol 
• 14609-79-1 2,2,4,4-tetramethyl-3-pentanol 
• 41902-42-5 tri-tert-butylcarbinol 

Relevant academic research and scientific papers

The effect Of Solvent on Competing Hydroperoxide and Dioxetane Formation on Photo-Sensitized Oxygenation of Olefins

The rates of the competitive photo-sensitized oxygenation of 2-isobutylidene-adamantane (1) and 2-propylidene-adamantane (2) with 1,1-di-t-butyl-2-methoxyethene (3) in various solvents were determined.The rates for 1 and 2 were independent of solvent, whereas that for 3 varied markedly with solvent polarity.Compounds 1 and 2 gave only hydroperoxides while 3 gave dioxetane.These results are interpreted in terms of two competing processes involving little and much charge separation leading to hydroperoxide and dioxetane, respectively.

Dehalogenation of 1,3-diiodotricyclo[3.3.0.03,7]octane: Generation of 1,3dehydrotricyclo[3.3.0.03,7]octane, a 2,5-methano-bridged [2.2.1]propellane

Compounds isolated from the reaction of (±)-1,3-diiodotricy-clo[3.3. 0.03,7]octane with molten sodium or tBuLi suggest the intermediate formation of (±)-1,3-dehydrotricyclo[3.3.0.03,7]octane. Worthy of note is the formation of stereoisomeric bi(5-methylenebicyclo[2.2.1]hept-2- ylidene) derivatives, probably by coupling of two units of (±)-1,3- dehydrotricyclo[3.3.0.03,7]octane of the same or different absolute configuration followed by fragmentation, processes that have been studied by theoretical calculations.

Alcohol oxidation via recyclable hydrophobic ionic liquid-supported IBX

The first ionic hydrophobic liquid-supported 1-hydroxy-1,2-benziodoxole-3(1H)-one-1-oxide (IBX) reagent was prepared for oxidizing alcohols. In this study, a hydrophobic ionic liquid-supported IBX reagent was synthesized and described. This hydrophobic ionic liquid-supported IBX reagent was able to be recovered and used in a recyclable reaction system by re-oxidation and washing.

New Organocatalyst scaffolds with high activity in promoting hydrazone and oxime formation at neutral pH

The discovery of two new classes of catalysts for hydrazone and oxime formation in water at neutral pH, namely 2-aminophenols and 2-(aminomethyl)benzimidazoles, is reported. Kinetics studies in aqueous solutions at pH 7.4 revealed rate enhancements up to 7-fold greater than with classic aniline catalysis. 2-(Aminomethyl)benzimidazoles were found to be effective catalysts with otherwise challenging aryl ketone substrates.

The retro Grignard addition reaction revisited: The reversible addition of benzyl reagents to ketones

The Grignard addition reaction is known to be a reversible process with allylic reagents, but so far the reversibility has not been demonstrated with other alkylmagnesium halides. By using crossover experiments it has been established that the benzyl addition reaction is also a reversible transformation. The retro benzyl reaction was shown by the addition of benzylmagnesium chloride to di-tert-butyl ketone followed by exchange of both the benzyl and the ketone moiety with another substrate. Similar experiments were performed with phenylmagnesium bromide and tert-butylmagnesium chloride, but in these two cases the Grignard addition reaction did not show any sign of a reverse transformation.

A reusable unsupported rhenium nanocrystalline catalyst for acceptorless dehydrogenation of alcohols through γ-C-H activation

Rhenium nanocrystalline particles (Re NPs), of 2 nm size, were prepared from NH4ReO4 under mild conditions in neat alcohol. The unsupported Re NPs convert secondary and benzylic alcohols to ketones and aldehydes, respectively, through catalytic acceptorless dehydrogenation (AD). The oxidant- and acceptor-free neat dehydrogenation of alcohols to obtain dihydrogen gas is a green and atom-economical process for making carbonyl compounds. Secondary aliphatic alcohols give quantitative conversion and yield. Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), Re K-edge X-ray absorption near-edge structure (XANES), and X-ray absorption fine structure (EXAFS) data confirmed the characterization of the Re NPs as metallic rhenium with surface oxidation to rhenium(IV) oxide (ReO2). Isotope labeling experiments revealed a novel γ-CH activation mechanism for AD of alcohols. Active particles: A rhenium nanoparticle (Re NP) catalyst is generated from NH4ReO4 under mild solution conditions in neat 3-octanol at 180°C. The resulting Re NPs catalyze acceptorless dehydrogenation of alcohols through a novel C-H activation pathway, and are fully recyclable. Copyright

Synthesis of sterically hindered ketones from aldehydes via O-silyl oximes

A mild and efficient method to synthesize sterically hindered ketones from aldehydes via O-silyl oximes was developed. Treatment of O-triphenylsilylated oximes with alkyl iodides in the presence of triethyl borane afforded the corresponding ketones.

Pivaloylmetals (tBu-COM: M=Li, MgX, K) as equilibrium components

Short-lived pivaloylmetals, (H3C)3C-COM, were established as the reactive intermediates arising through thermal heterolytic expulsion of O=CtBu2 from the overcrowded metal alkoxides tBuC(=O)-C(-OM)tBu2 (M=MgX, Li, K). In all three cases, this fission step is counteracted by a faster return process, as shown through the trapping of tBu-COM by O=C(tBu)-C(CD3)3 with formation of the deuterated starting alkoxides. If generated in the absence of trapping agents, all three tBu-COM species "dimerize" to give the enediolates MO-C(tBu)=C(tBu)-OM along with O=CtBu2 (2 equiv). A common-component rate depression by surplus O=CtBu2 proves the existence of some free tBu-COM (separated from O=CtBu2); but companion intermediates with the traits of an undissociated complex such as tBu-COM & O=CtBu2 had to be postulated. The slow fission step generating tBu-COMgX in THF levels the overall rates of dimerization, ketone addition, and deuterium incorporation. Formed by much faster fission steps, both tBu-COLi and tBu-COK add very rapidly to ketones and dimerize somewhat slower (but still fairly fast, as shown through trapping of the emerging O=CtBu2 by H3CLi or PhCH2K, respectively). At first sight surprisingly, the rapid fission, return, and dimerization steps combine to very slow overall decay rates of the precursor Li and K alkoxides in the absence of trapping agents: A detailed study revealed that the fast fission step, generating tBu-COLi in THF, is followed by a kinetic partitioning that is heavily biased toward return and against the product-forming dimerization. Both tBu-COLi and tBu-COK form tBu-CH=O with HN(SiMe3)3, but only tBu-COK is basic enough for being protonated by the precursor acyloin tBuC(=O)-C(-OH)tBu2. Copyright

A general route to fully terminally tert-butylated linear polyenes

Starting from the readily available α,β-unsaturated ketone, 3-tert-butyl4,4-dimethyl-2-pentenal, higher vinylogues, and fully terminally tert-butylated polyolefins with up to 13 consecutive conjugated double bonds have been prepared by either McMurry dimerization or Wittig chain-elongation routes. The highly unsaturated conjugated π systems, which show a remarkable stability, have been characterized by spectroscopic methods and, in many cases, by X-ray structural analysis. The yields are high enough to allow for thorough chemical reactivity studies.

Reaction of 3,3-di-tert-butylthiirane-2-thione S-oxide (α-dithiolactone S-oxide): synthesis of thiolato sulfinato-platinum and palladium complexes

Thermolysis of 3,3-di-tert-butylthiirane-2-thione S-oxide 4 gave di-tert-butyl ketone 5 and carbon disulfide (CS2). Treatment of α-dithiolactone S-oxide 4 with excess m-CPBA or triphenylphosphine gave di-tert-butylthioketene S-oxide 3 almost quantitatively. Treatment of 4 with (η2-ethylene)bis(triphenylphosphine)platinum(0) 13 or tetrakis(triphenylphosphine) palladium 17 resulted in the formation of thiolato sulfinato-platinum complex 15 or palladium complex 18, respectively. The structure of complex 15 was determined by X-ray crystallographic analysis.