6-((2-Methyl-1-oxoallyl)amino)hexanoic acid → HCID 58173699, compound

HRID 2280187Notes

Reaction equation

HRID 2280187 reaction equation
[C:1]([NH:6][CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][C:12]([OH:14])=O)(=[O:5])[C:2]([CH3:4])=[CH2:3].Br.[C:16]([O:20][C:21]([CH2:23][N:24]1[CH2:35][CH2:34][NH:33][CH2:32][CH2:31][N:30]([CH2:36][C:37]([O:39][C:40]([CH3:43])([CH3:42])[CH3:41])=[O:38])[CH2:29][CH2:28][N:27]([CH2:44][C:45]([O:47][C:48]([CH3:51])([CH3:50])[CH3:49])=[O:46])[CH2:26][CH2:25]1)=[O:22])([CH3:19])([CH3:18])[CH3:17].Cl.C(N=C=NCCCN(C)C)C>ClCCl>[C:16]([O:20][C:21](=[O:22])[CH2:23][N:24]1[CH2:35][CH2:34][N:33]([C:12](=[O:14])[CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][NH:6][C:1](=[O:5])[C:2]([CH3:4])=[CH2:3])[CH2:32][CH2:31][N:30]([CH2:36][C:37]([O:39][C:40]([CH3:41])([CH3:42])[CH3:43])=[O:38])[CH2:29][CH2:28][N:27]([CH2:44][C:45]([O:47][C:48]([CH3:51])([CH3:50])[CH3:49])=[O:46])[CH2:26][CH2:25]1)([CH3:17])([CH3:18])[CH3:19]

Participants

5

Reactant 3

HCID 1009776-((2-Methyl-1-oxoallyl)amino)hexanoic acidHCID 27239391,3-Propanediamine, N'-(ethylcarbonimidoyl)-N,N-dimethyl-, monohydrochloride2×HCID 21832608Tri-tert-butyl 2,2',2''-(1,4,7,10-tetraazacyclododecane-1,4,7-triyl)triacetate--hydrogen bromide (1/1)

Product 1

HCID 58173699HCID 58173699, compoundYield 113.8%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
-5 °C

Procedure

A suspension of 6-(methacryloylamino)caproic acid (2.80 g, 14.0 mmol), 1,4,7-tris(tert-butoxycarbonylmethyl)-1,4,7,10-tetraazacyclododecane hydrobromide (7.75 g, 13.0 mmol), N,N-dimethylaminopyridine (1.83 g, 15.0 mmol) and 5 mg BHT in 60 ml dichloromethane was cooled to −5° C. and 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (2.88 g, 15.0 mmol) was added portionwise under stirring. To complete the reaction, the mixture was stirred for 2 h at −5° C. and over night at room temperature. 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (1.00 g, 6.44 mmol) and N,N-dimethylaminopyridine (0.6 g, 4.9 mmol) each time were then added 3 more times at intervals of 2 h and finally left to be stirred for 6 h. The solution was washed 3 times with in each case 50 ml saturated aqueous NaCl solution, dried over anhydrous Na2SO4, filtered, concentrated on the rotary evaporator after the addition of 5 mg BHT and dried under fine vacuum. 10.3 g of a yellowish oil was obtained which was purified twice by chromatography (silica gel 60, 0.015-0.040 mm, acetone). The acetone was again distilled off on the rotary evaporator after the addition of 5 mg BHT and the product dried in fine vacuum. 6.13 g (8.8 mmol, 68% yield) of a yellow, highly viscous oil was obtained (HPLC purity: 95%).

Workup

  1. customthe reaction
  2. stirringthe mixture was stirred for 2 h at −5° C. and over night at room temperature
  3. waitfinally left
  4. stirringto be stirred for 6 h
  5. washThe solution was washed 3 times with in each case 50 ml saturated aqueous NaCl solution
  6. dry with materialdried over anhydrous Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated on the rotary evaporator
  9. additionafter the addition of 5 mg BHT
  10. customdried under fine vacuum

Sources & evidence

ORD record
ord-22b3e519ba3d4885a1328883ebb56bcc
Source dataset
uspto-grants-2015_09
Patent number
US09138382B2

Reaction notes

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