Hydrochloric Acid → HCID 67896019, compound

HRID 1196666Notes

Reaction equation

HRID 1196666 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:12]3[CH2:13][CH2:14][CH:15]([C:17]([OH:19])=[O:18])[CH2:16][C:11]=3[O:10][N:9]=2)=[CH:4][CH:3]=1.[CH:20]([N-]C(C)C)(C)C.[Li+].C([Li])CCC.C(NC(C)C)(C)C.CI.Cl>O1CCCC1.CCCCCC.O>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[C:12]3[CH2:13][CH2:14][C@@H:15]([C:17]([OH:19])=[O:18])[C@H:16]([CH3:20])[C:11]=3[O:10][N:9]=2)=[CH:6][CH:7]=1

Participants

10

Reactant 6

HCID 313Hydrochloric AcidHCID 6328Methyl iodideHCID 7912DiisopropylamineHCID 2724682Lithium diisopropylamideHCID 19898995HCID 19898995, compoundHCID 178418339Butyllithium

Product 1

HCID 67896019HCID 67896019, compound

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Conditions

Temperature
20 °C

Procedure

A solution of 3.46 g (0.0125 mol) of racemic 3-(4-chlorophenyl)-4,5,6,7-tetrahydro-1,2-benzisoxazole-6-carboxylic acid in 50 ml of dry tetrahydrofuran was added slowly at -70° C. to a solution of lithium diisopropylamide prepared by adding 10 ml of a 2.5M solution of n-butyllithium in hexane to 2.53 g (0.025 mol) of diisopropyl amine in 25 ml of dry tetrahydrofuran at -70° C. After 15 minutes, 2 g (0.014 mol) of methyl iodide were added and the mixture was allowed to warm to 20° C. over a period of 1.5 hours. The mixture was added to water, acidified with 2N hydrochloric acid and extracted with diethyl ether. The resulting mixture of cis- and trans-3-(4-chlorophenyl)-4,5,6,7-tetrahydro-7-methyl-1,2-benzisoxazole-6-carboxylic acids was separated by repeated crystallization from acetic acid. The cis-3-(4-chlorophenyl)-4,5,6,7-tetrahydro-7-methyl-1,2-benzisoxazole-6-carboxylic acid separated first, there being obtained 0.78 g of melting point 238°-241° C. The mother liquor yielded 0.79 g of trans-3-(4-chlorophenyl)-4,5,6,7-tetrahydro-7-methyl-1,2-benzisoxazole-6-carboxylic acid of melting point 183°-186° C.

Workup

  1. customprepared
  2. extractionextracted with diethyl ether
  3. additionThe resulting mixture of cis- and trans-3-(4-chlorophenyl)-4,5,6,7-tetrahydro-7-methyl-1,2-benzisoxazole-6-carboxylic acids
  4. customwas separated
  5. customcrystallization from acetic acid
  6. customThe cis-3-(4-chlorophenyl)-4,5,6,7-tetrahydro-7-methyl-1,2-benzisoxazole-6-carboxylic acid separated first
  7. customthere being obtained 0.78 g of melting point 238°-241° C

Sources & evidence

ORD record
ord-4d8a0f0a6c234f7dbf49d68cf7367613
Source dataset
uspto-grants-1992_05
Patent number
US05114960

Reaction notes

Loading…