(+)-10-CAMPHORSULFONIMINE

(+)-10-CAMPHORSULFONIMINE Property

Melting point:

229-230 °C(lit.)

Boiling point:

337℃

Density 

1.50

refractive index 

31 ° (C=2, CHCl3)

Flash point:

158℃

storage temp. 

Sealed in dry,Room Temperature

solubility 

Acetone, Dichloromethane, Hot Methanol

pka

-1.63±0.40(Predicted)

form 

Solid

color 

White Cyrstalline

InChI

InChI=1S/C10H15NO2S/c1-9(2)7-3-4-10(9)6-14(12,13)11-8(10)5-7/h7H,3-6H2,1-2H3/t7-,10-/m0/s1

InChIKey

ZAHOEBNYVSWBBW-XVKPBYJWSA-N

SMILES

N1=C2[C@@]3(C(C)(C)[C@]([H])(C2)CC3)CS1(=O)=O

CAS DataBase Reference

107869-45-4

Safety

Hazard Codes 

Xi

Risk Statements 

36/37/38

Safety Statements 

26-36

WGK Germany 

3

HS Code 

2934.99.9001

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

P261Avoid breathing dust/fume/gas/mist/vapours/spray.

P264Wash hands thoroughly after handling.

P264Wash skin thouroughly after handling.

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

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

(+)-10-CAMPHORSULFONIMINE Chemical Properties,Usage,Production

Chemical Properties

White Cyrstalline Solid

Uses

A useful synthetic intermediate. Used for asymmetric hydroxylation.

Uses

(+)-10-CAMPHORSULFONIMINE is a useful synthetic intermediate,it is used for asymmetric hydroxylation.

Synthesis

Example 1; Synthesis of (1R)-(+)-2,10-camphorsulfonamide (Scheme 3,3-1): Thionyl chloride (0.896 kg, 7.5 mol) was slowly added to a solution of (-)-camphorsulfonic acid (1.45 kg, 6.25 mol) in chloroform (7 L) over a period of 1 hour under refluxing conditions. The reaction mixture was refluxed for 16 h and then cooled to 4 °C using an ice bath. The cooled reaction mixture was slowly added to concentrated NH4OH (15 L) while controlling the rate of addition to keep the temperature below 15 °C. After the addition was completed, the mixture was stirred at room temperature for 4 hours. The organic layer was separated and the aqueous layer was extracted with chloroform (2 x 2 L). The combined organic extracts were washed with brine (4 L) and dried over MgSO4. After filtration, the filtrate was concentrated in vacuum and dried to give 1.2 kg (83% yield) of camphorsulfonamide. In another experiment, a comparable yield was obtained using 145 g scale of camphorsulfonamide with dichloromethane replacing chloroform for reaction and extraction. To a suspension of camphorsulfonamide (1.2 kg, 5.2 mol) in toluene (15 L) was added Amberlyst H+ resin (150 g), and the mixture was heated and refluxed for 4 hr while the resulting water was removed by azeotropic boiling using a Dean-Stark water separator. The reaction mixture was hot filtered to remove the resin. Cooling of the filtrate yielded a white solid, which was collected by filtration to give 1.02 kg (92% yield) of the target imine. To an ethanol (0.75 L) solution of the above imine (100 g, 0.47 mol) was added Raney nickel (100 g) and the mixture was hydrogenated at 40 psi for 2 hours. The catalyst was removed by filtration and the filtrate was concentrated in vacuum to give product 3-1 as a white solid.

References

[1] Tetrahedron, 1986, vol. 42, # 14, p. 4035 - 4044
[2] Chemical Communications, 1998, # 15, p. 1549 - 1550
[3] Journal of the American Chemical Society, 1988, vol. 110, p. 8477
[4] Patent: US2006/128789, 2006, A1. Location in patent: Page/Page column 7
[5] Organic Process Research and Development, 2005, vol. 9, # 2, p. 193 - 197