Thionyl Chloride → HCID 13689056, compound

HRID 364193Notes

Reaction equation

HRID 364193 reaction equation
Cl.[CH2:2]([N:4]([CH2:29][CH3:30])[CH2:5][CH2:6][N:7]1[C:15]2[CH:14]=[CH:13][C:12]([N+:16]([O-:18])=[O:17])=[C:11]3[S:19][C:20]4[C:25]([O:26][CH3:27])=[CH:24][CH:23]=[C:22]([OH:28])[C:21]=4[C:9]([C:10]=23)=[N:8]1)[CH3:3].Cl[C:32]1C2C(=O)C3C(=C(OC)C=CC=3O)SC=2C([N+]([O-])=O)=CC=1.ClC1C=CC([N+]([O-])=O)=C(SC2C(OC)=CC=C(OC)C=2C(O)=O)C=1.S(Cl)(Cl)=O.[Al+3].[Cl-].[Cl-].[Cl-]>C1(C)C=CC=CC=1>[CH2:29]([N:4]([CH2:2][CH3:3])[CH2:5][CH2:6][N:7]1[C:15]2[CH:14]=[CH:13][C:12]([N+:16]([O-:18])=[O:17])=[C:11]3[S:19][C:20]4[C:25]([O:26][CH3:27])=[CH:24][CH:23]=[C:22]([O:28][CH3:32])[C:21]=4[C:9]([C:10]=23)=[N:8]1)[CH3:30]

Participants

7

Reactant 5

HCID 24386Thionyl ChlorideHCID 6451240Aluminum(III) ChlorideHCID 20240171HCID 20240171, compoundHCID 20240207HCID 20240207, compoundHCID 178464048HCID 178464048, compound

Product 1

HCID 13689056HCID 13689056, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
70 °C

Procedure

Other 10-hydroxy-7-methoxy-, 10-methoxy-7-hydroxy-, and 7,10-dimethoxy-5-nitro-2-(substituted)-2H[1]benzothiopyrano[4,3,2-cd]indazoles can be prepared in the manner of Examples 33 through 35 and 54. One such compound is 2-[2-(diethylamino)-ethyl]-7-methoxy-5-nitro-2H[1]benzothiopyrano[4,3,2-cd]indazol-10-ol, hydrochloride salt, mp 267°-270° C. The latter compound is prepared from 1-chloro-5-methoxy-8-hydroxy-4-nitro-9H-thioxanthen-9-one which in turn is prepared as follows: A suspension of 5.8 g (0.016 mol) of 2-[(5-chloro-2-nitrophenyl)thio]-3,6-dimethoxybenzoic acid, 50 ml of toluene, and 3.8 g (0.032 mol) of thionyl chloride was heated under reflux for two hours, concentrated to dryness in vacuo, and dissolved in 50 ml of nitrobenzene. The solution was treated portionwise with 3.6 g (0.026 mol) of AlCl3, keeping the temperature below 35° C. during the addition. The mixture was stirred for two hours at 70° C., chilled in a refrigerator overnight, and poured into 400 ml of ice-cold H2O. The mixture was extracted four times with CH2Cl2 and the extracts were combined, dried (MgSO4), and concentrated in vacuo to dryness. The residue was triturated successively in petroleum ether and hot MeOH, and recrystallized from DMF to give 1.2 g of product, 272°-273° C.

Workup

  1. customis prepared
  2. temperaturewas heated
  3. temperatureunder reflux for two hours
  4. concentrationconcentrated to dryness in vacuo
  5. dissolutiondissolved in 50 ml of nitrobenzene
  6. customthe temperature below 35° C.
  7. additionduring the addition
  8. temperaturechilled in a refrigerator overnight
  9. extractionThe mixture was extracted four times with CH2Cl2
  10. dry with materialdried (MgSO4)
  11. concentrationconcentrated in vacuo to dryness
  12. customThe residue was triturated successively in petroleum ether
  13. customhot MeOH, and recrystallized from DMF

Sources & evidence

ORD record
ord-bdf54473b13e4b3cb2b82521d880a4b6
Source dataset
uspto-grants-1986_08
Patent number
US04604390

Reaction notes

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