Triisopropyl phosphite → HCID 54415170, compound

HRID 487487Notes

Reaction equation

HRID 487487 reaction equation
Br[CH2:2][C:3]([CH2:14][CH2:15][CH2:16][O:17][CH2:18][C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:4][CH:5]([NH:11][CH:12]=[O:13])[C:6]([O:8][CH2:9][CH3:10])=[O:7].[P:24]([O:33]C(C)C)([O:29][CH:30]([CH3:32])[CH3:31])[O:25][CH:26]([CH3:28])[CH3:27]>>[CH2:22]([O:21][C:19]([CH2:18][O:17][CH2:16][CH2:15][CH2:14][C:3]([CH2:2][P:24]([O:29][CH:30]([CH3:32])[CH3:31])([O:25][CH:26]([CH3:28])[CH3:27])=[O:33])=[CH:4][CH:5]([NH:11][CH:12]=[O:13])[C:6]([O:8][CH2:9][CH3:10])=[O:7])=[O:20])[CH3:23]

Participants

3

Reactant 2

HCID 8304Triisopropyl phosphiteHCID 53648515HCID 53648515, compound

Product 1

HCID 54415170HCID 54415170, compound

Procedure

5 g (15.1 mmol) of ethyl 7-ethoxycarbonylmethoxy-2-formylamino-3-hydroxy-4-methylene-heptanoate are dissolved in 50 ml of CH2Cl2 and 1.4 ml (18.1 mmol) of thionyl bromide are added dropwise at room temperature. After 2 hours 50 ml of water are added and the batch is stirred vigorously for 10 minutes. The organic phase is separated and washed once with water, once with a 1N solution of KHCO3 and twice with water. The aqueous phases are extracted once with CH2Cl2. The combined phases are dried over Na2SO4, filtered, and the filtrate is concentrated by evaporation giving ethyl 4-bromomethyl-7-ethoxycarbonylmethoxy-2-formylamino-hept-3-enoate as a yellow oil which is further reacted without purification. 6.4 g (15 mmol) of ethyl 4-bromomethyl-7-ethoxycarbonylmethoxy-2-formylamino-hept-3-enoate and 14.8 ml (60 mmol) of triisopropyl phosphite (90%) are heated to 80° C. and stirred for 18 hours under a pressure of 100 mbar. Excess triisopropyl phosphite is removed by distillation and the residue is chromatographed over silica gel with hexane/ethyl acetate (1:2:5%) to give ethyl 7-ethoxycarbonylmethoxy-2-formylamino-4-diisopropylphosphonomethyl-hept-3-enoate as a brown oil.

Workup

  1. customis further reacted without purification
  2. customExcess triisopropyl phosphite is removed by distillation
  3. customthe residue is chromatographed over silica gel with hexane/ethyl acetate (1:2:5%)

Sources & evidence

ORD record
ord-23448555514f422e935931816a0dc105
Source dataset
uspto-grants-1994_03
Patent number
US05294734

Reaction notes

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