815-24-7

Basic information

• Product Name: HEXAMETHYLACETONE
• Synonyms: 2,2,4,4-TETRAMETHYL-3-PENTANONE;HEXAMETHYLACETONE;DI-TERT-BUTYL KETONE;PIVALONE;(t-C4H9)2CO;2,2,4,4-tetramethyl-3-pentanon;2,2,4,4-Tetramethyl-pentan-3-one;2,2,4,4-tetramethylpentan-3-one
• CAS NO: 815-24-7
• Molecular Formula: C₉H₁₈O
• Molecular Weight: 142.24
• EINECS: 212-419-8
• Mol File: 815-24-7.mol
• Article Data: 38

Chemical Properties

• Melting Point: 152-153
• Boiling Point: 152-153 °C(lit.)
• Flash Point: 91 °F
• Appearance: Clear colorless/Liquid
• Density: 0.824 g/mL at 25 °C(lit.)
• Vapor Pressure: 3.53mmHg at 25°C
• Refractive Index: n20/D 1.419(lit.)
• Stability: Stable. Flammable. Incompatible with strong oxidizing agents.
• BRN: 1701122
• CAS DataBase Reference: HEXAMETHYLACETONE(CAS DataBase Reference)
• NIST Chemistry Reference: HEXAMETHYLACETONE(815-24-7)
• EPA Substance Registry System: HEXAMETHYLACETONE(815-24-7)

Safety Data

• Hazard Codes: F
• Statements: 10
• Safety Statements: 23-24/25
• RIDADR: UN 1224 3/PG 3
• WGK Germany: 3
• TSCA: T
• HazardClass: 3.2
• PackingGroup: III
• Hazardous Substances Data: 815-24-7(Hazardous Substances Data)

Usage

Chemical Properties

colourless liquid

Uses

Hexamethylacetone is used to prepare di-tert.-butyladamantylcarbinol by reacting with 1-bromo-adamantane.

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

General Description

The Microtox EC50 values for 2,2,4,4-tetramethyl-3-pentanone has been reported. The kinetics, stoichiometry and products of the reduction reaction of 2,2,4,4-tetramethyl-3-pentanone using lithium triethylborohydride under standard conditions (tetrahydrofuran, 0°C) has been examined.

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

Upstream product

• 5857-36-3 2,2,4-trimethylpentanone 
• 507-20-0 tertiary butyl chloride 
• 598-98-1 Methyl pivalate 
• 61065-35-8 2,3,4,4-tetramethyl-pentane-2,3-diol 
• 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 
• 54396-68-8 3-diazo-2,2,4,4-tetramethylpentane 
• 33581-95-2 tert-butylsulfamyl chloride 
• 35895-37-5 2,4-dimethyl-3-iodopent-2-ene 

Downstream Products

• 5857-69-2 2,2,3,4,4-pentamethyl-3-pentanol 
• 41902-42-5 tri-tert-butylcarbinol 
• 20818-90-0 p-Nitro-benzoesaeure-1,1-di-tert-butyl-2,2-dimethyl-propylester 
• 29772-39-2 2,2,3,4-tetramethyl-3-pentanol 
• 75-28-5 Isobutane 
• 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 

Relevant articles and documents

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.

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.

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