Methanol → (4-Amino-butyl)-(4-tert-butoxycarbonylamino-butyl)-carbamic acid tert-butyl ester

HRID 1503086Notes

Reaction equation

HRID 1503086 reaction equation
C1C(C(NCCCNCCCCNC(C[C:22](O)([C:46](O)=O)[CH2:23][C:24]([NH:26][CH2:27][CH2:28][CH2:29][CH2:30][NH:31]CCCNC(C2C=CC(O)=C(O)C=2)=O)=O)=O)=O)=CC(O)=C(O)C=1.[C:52]([O-:55])([O-:54])=O.[K+].[K+].C1(C(Cl)=O)[CH:63]=[C:62]([C:64](Cl)=O)[CH:61]=C(C(Cl)=O)C=1.[NH4+:73].[OH-:74].[CH3:75][OH:76]>C(Cl)Cl.O>[C:62]([O:74][C:75](=[O:76])[N:26]([CH2:24][CH2:23][CH2:22][CH2:46][NH2:73])[CH2:27][CH2:28][CH2:29][CH2:30][NH:31][C:52]([O:55][C:62]([CH3:61])([CH3:63])[CH3:64])=[O:54])([CH3:64])([CH3:63])[CH3:61]

Participants

8

Reactant 5

HCID 887MethanolHCID 11430Potassium CarbonateHCID 14923Ammonium HydroxideHCID 78138Trimesoyl chlorideHCID 11411510Petrobactin

Product 1

HCID 86761292(4-Amino-butyl)-(4-tert-butoxycarbonylamino-butyl)-carbamic acid tert-butyl ester

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6344DichloromethaneSolvent3×

Conditions

Temperature
0 °C

Procedure

A solution of (4-Amino-butyl)-(4-tert-butoxycarbonylamino-butyl)-carbamic acid tert-butyl ester 12 (460 mg, 1.28 mmol) and CH2Cl2 (3 mL) was prepared. Note: 12 is a known compound (ref: “Total Synthesis of Petrobactin and Its Homologues as Potential Growth Stimuli for Marinobacter hydrocarbonoclasticus, an oil-degrading bacteria.” Gardner, R. A.; Kinkade, R.+; Wang, C.; Phanstiel IV, O. J. Org. Chem. 2004, 69, 3530-3537). A solution of K2CO3 (420 mg, 3.04 mmol) and water (5 mL) was added to the original mixture. Aliquat (0.10 mL) was added and the mixture was cooled to 0° C. 1,3,5-benzenetricarboxylic acid chloride 11 (105 mg, 0.395 mmol) in CH2Cl2 (6 mL) was added dropwise to the original mixture and allowed to gradually warm and stir vigorously at rt for 6 hours. TLC (95% CH2Cl2, 4% MeOH, 1% NH4OH Rf=0.35) was used to monitor the reaction. After the reaction was complete, the aqueous layer was extracted three times in CH2Cl2 and saturated Na2CO3. The organic layers were combined and dried over anhydrous Na2SO4, filtered, and concentrated to give 590 mg of crude product. The crude was subjected to flash column chromatography (95% CH2Cl2, 4% MeOH, 1% NH4OH Rf=0.35) to give 13 (382 mg, 0.310 mmol, 78%). 1H NMR (CDCl3): δ 8.41 (s, 3H), 4.75 (br s, 3H), 3.49 (m, 6H), 3.23-3.06 (m, 18H), 2.78-1.30 (m, 78H).

Workup

  1. additionAliquat (0.10 mL) was added
  2. temperatureto gradually warm
  3. customthe reaction
  4. extractionthe aqueous layer was extracted three times in CH2Cl2
  5. dry with materialdried over anhydrous Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customto give 590 mg of crude product

Sources & evidence

ORD record
ord-dd447c3b8d694f819ee53f05e94b241c
Source dataset
uspto-grants-2015_12
Patent number
US09212131B2

Reaction notes

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