Carbon Dioxide → HCID 21941145, compound

HRID 431440Notes

Reaction equation

HRID 431440 reaction equation
[Br:1][C:2]1[CH:3]=C(N)C(=[C:8]([Br:10])[CH:9]=1)OC.[C:12](=O)(O)[O-:13].[C:16](Cl)(Cl)=[S:17].C(=O)=O.[C:23](#[N:25])[CH3:24]>C(Cl)Cl>[CH3:12][O:13][C:24]1[CH:3]=[C:2]([Br:1])[CH:9]=[C:8]([Br:10])[C:23]=1[N:25]=[C:16]=[S:17]

Participants

7

Reactant 5

HCID 280Carbon DioxideHCID 769Bicarbonate IonHCID 6342AcetonitrileHCID 10040ThiophosgeneHCID 133995463,5-Dibromo-2-methoxyaniline

Product 1

HCID 21941145HCID 21941145, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

In a flask under argon were placed 19.75 grams of 4,6-dibromo-o-anisidine (70 mmol) and 20 grams of solid bicarbonate. A large, heavy-duty magnetic stir bar was added, followed by 120 ml acetonitrile and 50 ml dichloromethane. The suspension was stirred at 0° C. as 6.0 ml of thiophosgene was added rapidly by syringe. A thick precipitate developed immediately. This was stirred vigorously as the contents of the flask were slowly warmed to room temperature. The carbon dioxide generated was led to a bubbler with a needle vent. The mixture thinned slightly as it warmed and was more easily stirred. Vigorous stirring was continued for two hours. The suspension was then recooled to 0° C. The solid was filtered off on a Buchner funnel, rinsing the flask and transferring any remaining solid with 30 ml of cold acetonitrile. The filtrate was rotary evaporated to a solid containing areas of orange discoloration. This solid was triturated with hexanes, pumped dry, and transferred to the Buchner funnel containing the white, original filter cake. This solid was washed with 5×100 ml portions of a 0.5 M aqueous solution of NaH2PO4 in order to neutralize the inorganic bicarbonate present (carbon dioxide was released). The solid was broken up during each rinse. The white product was then washed liberally with water and dried in vacuo. The dry product weighed 21.8 grams. Analytical data obtained from a similarly synthesized product were in agreement with the above-titled structure. NMR(300 MHz/CDCl3) data was: δ 3.92(s, 3H), 6.98(d, 1H), 7.31 (d, 1H). IR(CH2Cl2/cm−1) data was: 3020, 2970, 2940, 2030(br), 1575, 1555, 1470, 1400, 1040, 935, 870, 840.

Workup

  1. customIn a flask under argon were placed
  2. additionA large, heavy-duty magnetic stir bar was added
  3. additionwas added rapidly by syringe
  4. temperaturewarmed
  5. stirringwas more easily stirred
  6. stirringVigorous stirring
  7. customwas then recooled to 0° C
  8. filtrationThe solid was filtered off on a Buchner funnel
  9. washrinsing the flask
  10. customThe filtrate was rotary evaporated to a solid
  11. additioncontaining areas of orange discoloration
  12. customThis solid was triturated with hexanes
  13. custompumped dry
  14. additioncontaining the white, original filter cake
  15. washThis solid was washed with 5×100 ml portions of a 0.5 M aqueous solution of NaH2PO4 in order
  16. washThe white product was then washed liberally with water
  17. customdried in vacuo
  18. customAnalytical data obtained from a similarly synthesized product

Sources & evidence

ORD record
ord-66b26576c5d74ae29e59d77cb29b27ca
Source dataset
uspto-grants-2003_12
Patent number
US06660529B2

Reaction notes

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