(2-AMINO-PHENYL)-CARBAMIC ACID TERT-BUTYL ESTER

(2-AMINO-PHENYL)-CARBAMIC ACID TERT-BUTYL ESTER Property

Melting point:

109-114 °C

Boiling point:

280.6±23.0 °C(Predicted)

Density 

1.152±0.06 g/cm3(Predicted)

storage temp. 

under inert gas (nitrogen or Argon) at 2–8 °C

solubility 

DMSO (Slightly), Methanol (Slightly)

form 

Solid

pka

13.47±0.70(Predicted)

color 

Light Yellow

InChI

InChI=1S/C11H16N2O2/c1-11(2,3)15-10(14)13-9-7-5-4-6-8(9)12/h4-7H,12H2,1-3H3,(H,13,14)

InChIKey

KCZFBLNQOSFGSH-UHFFFAOYSA-N

SMILES

C(OC(C)(C)C)(=O)NC1=CC=CC=C1N

Safety

Hazard Codes 

Xi,Xn

Risk Statements 

22-43

Safety Statements 

36/37

WGK Germany 

3

HS Code 

2921490090

Hazard and Precautionary Statements (GHS)

Symbol(GHS)

Signal word

Warning

Hazard statements

H302Harmful if swallowed

H317May cause an allergic skin reaction

Precautionary statements

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

(2-AMINO-PHENYL)-CARBAMIC ACID TERT-BUTYL ESTER Chemical Properties,Usage,Production

Chemical Properties

White Solid

Uses

Protected 1,2-Phenyldiamine, an intermediate in the synthesis of histone deacetylase agents and antitumor agents.

Synthesis

General procedure for the synthesis of tert-butyl 2-aminophenylcarbamate from di-tert-butyl dicarbonate and o-phenylenediamine: 1. In a dry reaction flask, o-phenylenediamine (22 g, 200 mmol) and triethylamine (30 mL) were dissolved in THF (150 mL) and stirred until completely dissolved. 2. Prepare a solution by dissolving di-tert-butyl dicarbonate (44 g, 200 mmol) in THF (50 mL). 3. Slowly add the di-tert-butyl dicarbonate solution prepared in step 2 dropwise to the solution in step 1 at room temperature, keeping stirring during the dropwise addition. 4. after the dropwise addition, continue to stir the reaction mixture at room temperature for 15 hours. 5. upon completion of the reaction, the reaction mixture was concentrated to remove most of the solvent. 6. Ethyl acetate was added to the concentrated mixture and the resulting white solid was collected by filtration. 7. 7. The collected solid was dried under reduced pressure to give 21 g tert-butyl 2-aminophenylcarbamate. 8. The filtrate was further concentrated to give another solid which was filtered with ethyl acetate and dried, again under reduced pressure, to give 11 g of tert-butyl 2-aminophenylcarbamate. 9. The two obtained products were combined to give an overall yield of 76%. Product characterization: 1H-NMR (400 MHz, DMSO-d6) δ 1.48 (s, 9H), 4.84 (s, 2H), 6.55 (td, J = 7.6, 1.4 Hz, 1H), 6.70 (dd, J = 7.6, 1.3 Hz, 1H), 6.86 (td, J = 7.6, 1.5 Hz, 1H), 7.20 (d, J = 7.6 Hz, 1H), 8.30 (br s, 1H).

Purification Methods

Purify the ester by crystallisation from CHCl3/hexane (1:1, v/v) and dry it in vacuo. [Seto et al. J Am Chem Soc 115 1321 1993, Seto et al. J Am Chem Soc 127 11442 2005.]

References

[1] Research on Chemical Intermediates, 2017, vol. 43, # 3, p. 1355 - 1363
[2] Comptes Rendus Chimie, 2010, vol. 13, # 5, p. 544 - 547
[3] Journal of the Chilean Chemical Society, 2013, vol. 58, # 1, p. 1619 - 1623
[4] Tetrahedron Letters, 2007, vol. 48, # 47, p. 8318 - 8322
[5] RSC Advances, 2016, vol. 6, # 82, p. 78576 - 78584