p-Toluenesulfonic acid monohydrate → (4-Methoxyphenyl)methyl amino(diethoxyphosphoryl)acetate

HRID 1657996Notes

Reaction equation

HRID 1657996 reaction equation
C(=[N:8][CH:9]([P:22]([O:27][CH2:28][CH3:29])([O:24][CH2:25][CH3:26])=[O:23])[C:10]([O:12][CH2:13][C:14]1[CH:19]=[CH:18][C:17]([O:20][CH3:21])=[CH:16][CH:15]=1)=[O:11])C1C=CC=CC=1.O.C1(C)C=CC(S(O)(=O)=O)=CC=1.NC(P(O)(ON(CC)CC)=O)C(OCC1C=CC(OC)=CC=1)=O>CCOCC>[NH2:8][CH:9]([P:22]([O:27][CH2:28][CH3:29])([O:24][CH2:25][CH3:26])=[O:23])[C:10]([O:12][CH2:13][C:14]1[CH:15]=[CH:16][C:17]([O:20][CH3:21])=[CH:18][CH:19]=1)=[O:11]

Participants

5

Reactant 3

HCID 521998p-Toluenesulfonic acid monohydrateHCID 53679829p-Methoxybenzyl alpha-amino-diethylaminophosphonoacetateHCID 53831774p-methoxybenzyl N-benzylidene-alpha-amino-diethylphosphonoacetate

Product 1

HCID 53833759(4-Methoxyphenyl)methyl amino(diethoxyphosphoryl)acetate

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

A solution of 16.4 g. of p-methoxybenzyl N-benzylidene-α-amino-diethylphosphonoacetate in 100 ml. of ether is added over 30 minutes with stirring to a solution of 8.25 g. of p-toluenesulfonic acid monohydrate in 150 ml. of ether. To the reaction mixture is added 60 ml. of cyclohexane and the solvent layer is separated by decantation. The residue is washed with additional 2:1 ether-cyclohexane and is again decanted. The resulting oil is dissolved in about 25 ml. of 1 M dipotassium phosphate (final pH about 7), and this solution is extracted 4 times with methylene chloride. The methylene chloride solution is then dried with magnesium sulfate, filtered and evaporated to give 12 g. of p-methoxybenzyl α-amino-diethylaminophosphonoacetate as an orange oily product. ir (neat) μ: 2.95 (NH), 5.75 (C=O), and 9.75 (P--O); nmr (CDCl3) τ: 8.73 (t, 6, J=7Hz, CH2CH3), 8.12 (s, 2, NH2), 6.18 (s, 3, ArOCH3), 6.03 (d, 1, J=21Hz, CH), 5.86 (p, 4, J=7Hz, CH2CH3), 4.80 (s, 2, ArCH2), 3.11 (d, 2, J=8Hz, arH), and 2.64 (d, 2, J=8Hz, ArH).

Workup

  1. additionTo the reaction mixture is added 60 ml
  2. customof cyclohexane and the solvent layer is separated by decantation
  3. washThe residue is washed with additional 2:1 ether-cyclohexane
  4. customis again decanted
  5. dissolutionThe resulting oil is dissolved in about 25 ml
  6. extractionof 1 M dipotassium phosphate (final pH about 7), and this solution is extracted 4 times with methylene chloride
  7. dry with materialThe methylene chloride solution is then dried with magnesium sulfate
  8. filtrationfiltered
  9. customevaporated
  10. customto give 12 g

Sources & evidence

ORD record
ord-b1f215b20d774a14b576b3f4aad9e765
Source dataset
uspto-grants-1976_06
Patent number
US03962224

Reaction notes

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