BENZYLOXYACETONE

BENZYLOXYACETONE Property

Boiling point:

259 °C (lit.)

Density 

1.04 g/mL at 25 °C (lit.)

refractive index 

n20/D 1.512(lit.)

Flash point:

>230 °F

storage temp. 

Inert atmosphere,Room Temperature

Appearance

Colorless to light yellow Liquid

InChI

InChI=1S/C10H12O2/c1-9(11)7-12-8-10-5-3-2-4-6-10/h2-6H,7-8H2,1H3

InChIKey

YHMRKVGUSQWDGZ-UHFFFAOYSA-N

SMILES

C(OCC1=CC=CC=C1)C(=O)C

Safety

WGK Germany 

3

Hazard and Precautionary Statements (GHS)

Symbol(GHS)

Signal word

Warning

Hazard statements

H315Causes skin irritation

H319Causes serious eye irritation

H335May cause respiratory irritation

Precautionary statements

P264Wash hands thoroughly after handling.

P264Wash skin thouroughly after handling.

P280Wear protective gloves/protective clothing/eye protection/face protection.

P302+P352IF ON SKIN: wash with plenty of soap and water.

P305+P351+P338IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continuerinsing.

P321Specific treatment (see … on this label).

P332+P313IF SKIN irritation occurs: Get medical advice/attention.

P362Take off contaminated clothing and wash before reuse.

BENZYLOXYACETONE Chemical Properties,Usage,Production

Uses

Benzyloxyacetone (1-Benzyloxy-2-propanone) may be used in the synthesis of:

• 7-benzyloxy-6-methyl-5-hepten-1-yne
• (Z)-2-methylhept-2-en-6-yn-1-o1
• (S)-(+)-1,2-propanediol, 1-benzyl ether

It may be used as a starting material in synthesizing (2S,4RS)-4-acetoxy-2-[(benzyloxy)methyl]-2-methyldioxolane and (2R,4RS)-4-acetoxy-2-[(benzyloxy)methyl]-2-methyldioxolane.

General Description

Benzyloxyacetone (α-Benzyloxyacetone) is an α-substituted acetone. It undergoes direct aldol reaction with 4-nitrobenzaldehyde in the presence of (S)-BINAM-L-prolinamide/benzoic acid to form predominantly the syn-diasteroisomer.

Synthesis

To a stirred mixed solution of allyl benzyl ether (0.4 mmol) in acetonitrile (3.5 mL) and water (0.5 mL) was added palladium dichloride (PdCl2, 3.6 mg, 0.02 mmol, 5 mol%) and chromium trioxide (CrO3, 20 mg, 0.6 mmol, 0.5 eq.), in that order, at room temperature. The reaction mixture was heated to 60°C and stirred in a closed flask for the indicated time (refer to Table 5-7). Upon completion of the reaction, the mixture was filtered through a small silica gel pad and washed with ethyl acetate (EtOAc), followed by concentration of the filtrate. In some cases, the residue is almost pure in the residue and no further purification is required. In the remaining cases, the residue needs to be purified by silica gel column chromatography using petroleum ether/ethyl acetate (EtOAc) as eluent to finally obtain benzyloxyacetone.

References

[1] Tetrahedron, 2014, vol. 70, # 32, p. 4760 - 4767
[2] Journal of Organic Chemistry, 2016, vol. 81, # 5, p. 2113 - 2121
[3] Journal of Organic Chemistry, 2014, vol. 79, # 12, p. 5787 - 5793
[4] Tetrahedron Letters, 2013, vol. 54, # 19, p. 2293 - 2295
[5] Tetrahedron Letters, 2009, vol. 50, # 24, p. 2893 - 2894