Sulfuric Acid → HCID 86739330, compound

HRID 1904106Notes

Reaction equation

HRID 1904106 reaction equation
[C:1](=[O:5])([O:3][CH3:4])[NH2:2].S(=O)(=O)(O)O.[CH3:11][C:12]([C:14]1[CH:19]=[CH:18][CH:17]=[C:16]([C:20]([CH3:22])=[CH2:21])[CH:15]=1)=[CH2:13].C(=O)([O-])[O-].[Na+].[Na+].CCCCCCCCCCCCCCCC.CCCCCCCCCCCCCCCCCCCCC.[N-]=C=O.[N-]=C=O.CC(C)C1C=CC=C(C(C)C)C=1.[N-]=C=O.C(C1C(C)=C(C)C=CC=1)(C)=C>>[N-:2]=[C:1]=[O:3].[NH2:2][C:1]([O:3][CH2:4][CH3:11])=[O:5].[CH3:21][CH:20]([CH3:22])[C:16]1[CH:17]=[CH:18][CH:19]=[C:14]([CH:12]([CH3:13])[CH3:11])[CH:15]=1

Participants

9

Reactant 8

HCID 1118Sulfuric AcidHCID 10340Sodium CarbonateHCID 11006HexadecaneHCID 11722Methyl CarbamateHCID 12403HeneicosaneHCID 773531,3-DiisopropenylbenzeneHCID 19005703HCID 19005703, compoundHCID 22639212HCID 22639212, compound

Product 1

HCID 86739330HCID 86739330, compoundYield 3%

Conditions

Temperature
60 °C

Procedure

To a flask containing 59.30 g (789.92 mmoles) of molten methyl carbamate (85° C. oil bath) was added 260 mg (2.6 mmole) of conc.sulfuric acid. The temperature of the oil bath was then lowered to 60° C., and 14.79 g (93.61 mmoles) of m-DIPEB added dropwise to the reaction mixture. The reaction mixture was stirred 60° C. for 4.5 hours, and 500 mg of anhydrous sodium carbonate added to neutralize the acid catalyst. The mixture was stirred at 60° C. for another 30 minutes and then distilled under the vacuum 95°/30 mm Hg) to recover unreacted methyl carbamate (44.05 g; >90% recovery). GLC analyses of the white residue showed that m-TMXDU and m-TMU were formed in 65% and 24% yields, respectively. The solid was then mixed with 50 g of hexadecane and 1.66 g of heneicosane (GLC internal standard), and the mixture cracked at 265° C. for 4 hours. GLC analyses indicated that α,α,α',α'-tetramethyl meta-xylene diisocyanate (m-TMXDI) (45%), meta-isopropenyldimethylbenzene isocyanate (m-TMI) (10%) and α,α,α',α'-tetramethyl-meta-xylene monourethane monoisocyanate (m-TMXUI) (3%) were formed based on the m-DIPEB.

Workup

  1. additionwas added 260 mg (2.6 mmole) of conc
  2. customwas then lowered to 60° C.
  3. stirringThe mixture was stirred at 60° C. for another 30 minutes
  4. distillationdistilled under the vacuum 95°/30 mm Hg)
  5. customto recover unreacted methyl carbamate (44.05 g; >90% recovery)
  6. customm-TMU were formed in 65% and 24%
  7. customyields
  8. waitthe mixture cracked at 265° C. for 4 hours

Sources & evidence

ORD record
ord-0540be32f00e467db27058557fc23e7c
Source dataset
uspto-grants-1984_03
Patent number
US04439616

Reaction notes

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