Hydrochloric Acid → HCID 178436646, compound

HRID 1598935Notes

Reaction equation

HRID 1598935 reaction equation
C(N(CC)CC)C.Cl[S:9]([C:12]1[CH:13]=[C:14]2[C:19](=[CH:20][CH:21]=1)[O:18][C:17](=[O:22])[C:16](=[N+:23]=[N-:24])[C:15]2=[O:25])(=[O:11])=[O:10].Cl.C1C[O:30]CC1>>[CH2:16]=[CH:15][C:14]1[CH:19]=[CH:20][C:21]([OH:30])=[CH:12][CH:13]=1.[N+:23](=[C:16]1[C:15](=[O:25])[C:14]2[C:19](=[CH:20][CH:21]=[C:12]([S:9]([O-:30])(=[O:11])=[O:10])[CH:13]=2)[O:18][C:17]1=[O:22])=[N-:24]

Participants

5

Reactant 4

HCID 313Hydrochloric AcidHCID 8028Tetrahydrofuran2×HCID 8471TriethylamineHCID 178514331HCID 178514331, compound

Product 1

HCID 178436646HCID 178436646, compoundYield 1,032.7%

Procedure

Example 8 illustrates the preparation of a partially substituted polymeric product with a photoactive compound. Example 3 was substantially repeated in Example 8 with the exception of modifications in procedure as set forth below. A 500 mL three-necked round-bottom flask equipped with a magnetic stirrer, water bath, thermometer, nitrogen inlet and bubbler was charged with a solution of PHS (13.3 g, 110 mmol based on monomer repeat units) in THF (170 g). Triethylamine (6.8 g) was added dropwise and the reaction mixture was allowed to stir for an additional 3-5 minutes. A solution of 6-chlorosulfonyl-3-diazo-4-oxo-3,4-dihydrocoumarin (1.6 g, 5.6 mmol) in THF (124 g) was added dropwise and the reaction was allowed to stir at room temperature. After one hour, HPLC analysis showed no residual starting material. The reaction mixture was cooled in an ice bath and neutralized by dropwise addition of cone. HCl (8 g) while maintaining the reaction temperature around 12° C. The reaction mixture was filtered to remove any insoluble impurities. The filtrate was precipitated, with stirring, into ten times its weight of hexane. The resulting slurry was filtered, dried in a vacuum oven overnight at 60° C.; yield 11.2 g of white solids (77% yield). The product was characterized by UV-Vis as follows: the UV-Vis absorption spectrum of the product in THF solvent was determined at a dilution factor, DF=46,948.36 yielding, λ1 max=230 nm, ε1 max=91,245.78 liters/mole cm; and λ2 max=282 nm, ε2 max=29,969.20 liters/mole cm (based on a repeat unit MW=2633.2).

Workup

  1. customthe preparation of a partially substituted polymeric product with a photoactive compound
  2. customA 500 mL three-necked round-bottom flask equipped with a magnetic stirrer, water bath
  3. stirringto stir at room temperature
  4. waitAfter one hour
  5. temperatureThe reaction mixture was cooled in an ice bath
  6. additionneutralized by dropwise addition of cone
  7. filtrationThe reaction mixture was filtered
  8. customto remove any insoluble impurities
  9. customThe filtrate was precipitated
  10. stirringwith stirring, into ten times its weight of hexane
  11. filtrationThe resulting slurry was filtered
  12. customdried in a vacuum oven overnight at 60° C.

Sources & evidence

ORD record
ord-7c726499687b4aa987faff20bbe23800
Source dataset
uspto-grants-1998_04
Patent number
US05739295

Reaction notes

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