Formic Acid → Phenyl carbamate

HRID 1837390Notes

Reaction equation

HRID 1837390 reaction equation
C(O)=O.[CH:4]([O:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)=[O:5].C(=O)(OC1C=CC=CC=1)OC1C=CC=CC=1.[CH3:29][C:30]1[CH:35]=[CH:34][C:33]([N:36]=C=O)=[CH:32][C:31]=1[N:39]=C=O>C1(O)C=CC=CC=1.CC1C=CC(N=C=O)=CC=1N=C=O.C1(C)C=CC=CC=1.O>[C:30]1([CH3:29])[C:31]([NH2:39])=[CH:32][C:33]([NH2:36])=[CH:34][CH:35]=1.[C:4]([O:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1)(=[O:5])[NH2:36]

Participants

10

Reactant 4

HCID 284Formic AcidHCID 7597Diphenyl carbonateHCID 11443Toluene 2,4-DiisocyanateHCID 74626Phenyl formate

Product 2

HCID 72612,4-DiaminotolueneHCID 69322Phenyl carbamateYield 79.9%

Reagents, catalysts & solvents 4

HCID 11443Toluene 2,4-DiisocyanateCatalystHCID 962WaterSolventHCID 996PhenolSolvent2×HCID 1140TolueneSolvent

Conditions

Temperature
232 °C

Procedure

The di-formamide of 2,4-toluene diamine is prepared by either reaction of the diamine with formic acid, with azeotropic removal of water with refluxing toluene, or by reaction of the diamine with phenyl formate in phenol. As in Example 1 above, the di-formamide (5.46 grams, 0.0307 mole) in phenol (17.50 grams, 0.186 mole) is added dropwise to diphenyl carbonate (26.40 grams, 0.123 mole) and heated to 232° C. at 110 mmHg. IS/GC analysis of the overhead (30.55 grams) and pot material (17.42 grams) shows the recovery of 4.004 grams of free 2,4-TDI and 0.277 grams of 2,4-TDI as phenol carbamate (0.0246 moles total TDI, 79.9% yield, based on di-formamide fed).

Sources & evidence

ORD record
ord-dcc672b21c1349f0831b7e392cdd816f
Source dataset
uspto-grants-2004_08
Patent number
US06781010B1

Reaction notes

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