Ethyl chloroformate → Tris(2-carbethoxyaminoethyl)amine

HRID 257147Notes

Reaction equation

HRID 257147 reaction equation
[CH2:1]([O:3][C:4](Cl)=[O:5])[CH3:2].[NH2:7][CH2:8][CH2:9][N:10]([CH2:14][CH2:15][NH2:16])[CH2:11][CH2:12][NH2:13].[OH-:17].[K+]>C1C=CC=CC=1.O>[C:4]([NH:7][CH2:8][CH2:9][N:10]([CH2:14][CH2:15][NH:16][C:4]([O:3][CH2:1][CH3:2])=[O:5])[CH2:11][CH2:12][NH:13][C:4]([O:3][CH2:1][CH3:2])=[O:17])([O:3][CH2:1][CH3:2])=[O:5]

Participants

6

Reactant 3

HCID 10928Ethyl chloroformate2×HCID 14797Potassium HydroxideHCID 77731Tris(2-aminoethyl)amine

Product 1

HCID 19784622Tris(2-carbethoxyaminoethyl)amineYield 85%

Reagents, catalysts & solvents 2

HCID 241BenzeneSolventHCID 962WaterSolvent2×

Conditions

Temperature
5 °C

Procedure

In accord with the procedure of H. Schmidt et al., Z. anoro. allq. Chem., 578, 75 (1989), ethylchloroformate (33.4 g, 0.310 mol) was added dropwise to a solution of tris(2-aminoethyl)amine (TREN) (29.2 g, 0.20 mol) dissolved in a mixture of benzene (225 mL) and water (100 mL) cooled to 5° C. After the addition was completed, KOH (36.4 g, 0.650 mol) dissolved in water (35 mL) was added dropwise simultaneously with more ethylchloroformate (33.4 g, 0.310 mol). The reaction mixture was stirred for 2 hr. at 5° C. and then for 8 hr. at room temperature. The benzene layer was separated and the water layer extracted with chloroform (2×100 mL). The combined organic fractions were dried over MgSO4, decanted and the decantate evaporated to dryness to give the intermediate tris(2-carbethoxyaminoethyl)amine (5) in 85% yield as a thick oil which was used in subsequent reactions without further purification (1H NMR (CDCl3)δ1.27 (9H, t, 3JHH =7.1 Hz), δ2.60 (6H, t, 3JHH =5.7 Hz), δ3.23 (6H, br), δ4.10 (6H, q, 3J=7.1 5.50 (3H, br); IR 3300, 1720, 1530, 1250 cm-1).

Workup

  1. additionAfter the addition
  2. waitat 5° C. and then for 8 hr
  3. customat room temperature
  4. customThe benzene layer was separated
  5. extractionthe water layer extracted with chloroform (2×100 mL)
  6. dry with materialThe combined organic fractions were dried over MgSO4
  7. customdecanted
  8. customthe decantate evaporated to dryness

Sources & evidence

ORD record
ord-b340bf4b24584c4cb0124093d080d9f6
Source dataset
uspto-grants-1993_11
Patent number
US05260436

Reaction notes

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