Sulfuric Acid → Trans-3-azido-1,2,3,4-tetrahydro-5-methoxy-2-naphthalinol

HRID 542173Notes

Reaction equation

HRID 542173 reaction equation
[CH3:1][O:2][C:3]1[CH:13]=[CH:12][CH:11]=[C:10]2[C:4]=1[CH2:5][CH:6]1[O:8][CH:7]1[CH2:9]2.[N-:14]=[N+:15]=[N-:16].[Na+].S(=O)(=O)(O)O.C(Cl)Cl>CS(C)=O>[N:14]([C@@H:6]1[CH2:5][C:4]2[C:10](=[CH:11][CH:12]=[CH:13][C:3]=2[O:2][CH3:1])[CH2:9][C@H:7]1[OH:8])=[N+:15]=[N-:16].[N:14]([C@@H:7]1[CH2:9][C:10]2[C:4](=[C:3]([O:2][CH3:1])[CH:13]=[CH:12][CH:11]=2)[CH2:5][C@H:6]1[OH:8])=[N+:15]=[N-:16]

Participants

7

Reactant 4

HCID 1118Sulfuric AcidHCID 6344DichloromethaneHCID 33557Sodium AzideHCID 151310673-Methoxy-1a,2,7,7a-tetrahydronaphtho[2,3-b]oxirene

Product 2

HCID 15131068Trans-3-azido-1,2,3,4-tetrahydro-5-methoxy-2-naphthalinolHCID 58024476trans-3-Azido-1,2,3,4-tetrahydro-8-methoxy-2-naphthalinol

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent4×

Procedure

30.0 g (0.170M) of 1a,2,7,7a-tetrahydro-3-methoxynaphth[2,3-b]oxirane are dissolved in dimethyl sulphoxide. Furthermore, 90.0 g (1.384M) of sodium azide are suspended in DMSO and 19.5 g (0.200M) of concentrated sulphuric acid are dissolved in DMSO. The total quantity of DMSO is 1000 ml. The solutions and supensions are combined. Stirring subsequently takes place for 15 hours at 60°. 1500 ml of methylene chloride are then added to the reaction mixture. A suspension is obtained, which is filtered over Hyflo. The rose solution is concentrated by evaporation at 60° (10 torr), then at 80° (high vacuum 1/100 torr). Trans-3-azido-1,2,3,4-tetrahydro-5-methoxy-2-naphthalinol (m.p. 83°-84°) and its structural isomer trans-3-azido-1,2,3,4-tetrahydro-8-methoxy-2-naphthalinol (m.p. 145°-147°) are obtained in a ratio of 1:1. The structural isomers are separated by fractional crystallisation (methylene chloride/hexane).

Workup

  1. customA suspension is obtained
  2. filtrationwhich is filtered over Hyflo
  3. concentrationThe rose solution is concentrated by evaporation at 60° (10 torr)
  4. customat 80°

Sources & evidence

ORD record
ord-8938eac4becc4f02ae89797291d74c53
Source dataset
uspto-grants-1987_04
Patent number
US04656167

Reaction notes

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