Phenol → 4,4-Diaminodiphenylmethane

HRID 1837391Notes

Reaction equation

HRID 1837391 reaction equation
C(=O)(OC1C=CC=CC=1)OC1C=CC=CC=1.C1(O)C=CC=CC=1.C1(O)C=CC=CC=1.C(OC1C=CC=CC=1)=O.C(OC1C=CC=CC=1)=O.[CH:49]1[C:54]([CH2:55][C:56]2[CH:61]=[CH:60][C:59]([N:62]=C=O)=[CH:58][CH:57]=2)=[CH:53][CH:52]=[C:51]([N:65]=C=O)[CH:50]=1.C(OC1C=CC=CC=1)(=O)N>C(O)=O>[CH2:55]([C:56]1[CH:61]=[CH:60][C:59]([NH2:62])=[CH:58][CH:57]=1)[C:54]1[CH:53]=[CH:52][C:51]([NH2:65])=[CH:50][CH:49]=1

Participants

8

Reactant 6

HCID 996Phenol2×HCID 7570Diphenylmethane diisocyanateHCID 7597Diphenyl carbonateHCID 69322Phenyl carbamateHCID 74626Phenyl formateHCID 88047488HCID 88047488, compound

Product 1

HCID 75774,4-DiaminodiphenylmethaneYield 91.6%

Reagents, catalysts & solvents 1

HCID 284Formic AcidSolvent

Procedure

The di-formamide of 4,4′-methylene-dianiline is prepared by the reaction of the diamine with 2.1 molar equivalents of formic acid, and removing the water byproduct by azeotropic distillation with toluene. Using the same apparatus as Example 1, but without the addition funnel, diphenyl carbonate (48.45 grams, 0.226 mole) and 4,4′-MDA-di-formamide (6.92 grams, 0.0272 mole), containing 0.21 grams of phenol, is heated to reflux at 38 mmHg. Reaction and phenol/phenyl formate distillation commences at a pot temperature of 155° C., and ceases 30 minutes later at a pot temperature of 195° C., 17 mmHg. IS/GC analysis of the condensate (10.55 grams) shows only phenyl formate, phenol and a trace of DPC. The pot material (43.97 grams) contains 3.02 grams of 4,4′-diphenylmethane diisocyanate (MDI) and 3.21 grams of MDI as the mono-phenol carbamate, a recovery of 0.0249 mole equivalents of MDI, equal to a 91.6% yield, based on di-formamide charged.

Workup

  1. customremoving the water byproduct
  2. distillationby azeotropic distillation with toluene
  3. temperatureis heated
  4. temperatureto reflux at 38 mmHg
  5. additioncharged

Sources & evidence

ORD record
ord-e815a674b88d4b5a8d8a339c841e6d21
Source dataset
uspto-grants-2004_08
Patent number
US06781010B1

Reaction notes

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