Diiodomethane → Ammonium Acetate

HRID 1470047Notes

Reaction equation

HRID 1470047 reaction equation
[CH2:1]([CH2:4][O:5]C)OC.[CH2:7]([Zn]CC)C.ICI.[C:15]([C:18]1[S:22]/[C:21](=[N:23]\[C:24]([C:26]23[CH2:33][CH:32]4[CH2:34][CH:28]([CH2:29][CH:30]2[CH2:31]4)[CH2:27]3)=[O:25])/[N:20]([CH2:35][CH2:36][O:37][CH3:38])[CH:19]=1)([CH3:17])=[CH2:16]>C(Cl)Cl>[C:4]([O-:5])(=[O:25])[CH3:1].[NH4+:20].[CH3:38][O:37][CH2:36][CH2:35][N:20]1[CH:19]=[C:18]([C:15]2([CH3:7])[CH2:17][CH2:16]2)[S:22]/[C:21]/1=[N:23]\[C:24]([C:26]12[CH2:33][CH:32]3[CH2:34][CH:28]([CH2:29][CH:30]1[CH2:31]3)[CH2:27]2)=[O:25]

Participants

7

Reactant 4

HCID 6346DiiodomethaneHCID 80711,2-DimethoxyethaneHCID 178418750HCID 178418750, compoundHCID 178439594HCID 178439594, compound

Product 2

HCID 517165Ammonium AcetateHCID 178495765HCID 178495765, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Conditions

Temperature
-10 °C

Procedure

A 20 mL vial was charged with 1 mL of CH2Cl2 and dimethoxyethane (78 μL, 0.75 mmol). The solution was cooled to −10° C. and diethylzinc (89 mg, 0.72 mmol) was added. To this solution was added diiodomethane (402 mg, 1.5 mmol) dropwise. After the addition was complete, the resulting clear solution was stirred for 10 minutes at −10° C. then a solution of Example 221C (65 mg, 0.19 mmol) in CH2Cl2 (0.5 mL) was added. The reaction mixture was stirred overnight at room temperature then quenched with water, and extracted with CH2Cl2. The organic extract was dried (Na2SO4), filtered and concentrated. Purification by preparative high pressure liquid chromotography on a Waters Symmetry C8 column (40 mm×100 mm, 7 μm particle size) using a gradient of 10% to 100% acetonitrile:ammonium acetate (10 mM) over 15 minutes at a flow rate of 70 mL/minutes afforded the title compound. 1H NMR (500 MHz, CDCl3) δ ppm 0.82 (t, J=6.71, 4.58 Hz, 2H) 0.91 (t, J=5.80, 5.19 Hz, 2H) 1.41 (s, 3H) 1.60-1.67 (m, 4H) 1.81-1.88 (m, 2H) 1.90 (dd, J=10.68, 2.75 Hz, 2H) 2.16 (dd, J=10.37, 0.92 Hz, 2H) 2.29-2.36 (m, 2H) 2.72 (t, J=6.71 Hz, 1H) 3.36 (s, 3H) 3.74 (t, J=4.88 Hz, 2H) 4.41 (t, J=4.88 Hz, 2H) 6.88 (s, 1H); MS (ESI) m/z 361 (M+H)+.

Workup

  1. additionAfter the addition
  2. stirringThe reaction mixture was stirred overnight at room temperature
  3. customthen quenched with water
  4. extractionextracted with CH2Cl2
  5. extractionThe organic extract
  6. dry with materialwas dried (Na2SO4)
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customPurification by preparative high pressure liquid chromotography on a Waters Symmetry C8 column (40 mm×100 mm, 7 μm particle size)

Sources & evidence

ORD record
ord-c9e3b4b1cc60405292abe2555e80a84d
Source dataset
uspto-grants-2015_04
Patent number
US09006275B2

Reaction notes

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