Water → HCID 54156421, compound

HRID 2082961Notes

Reaction equation

HRID 2082961 reaction equation
[CH3:1][CH:2]([CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])[CH:3]([C:5]1[CH:6]=[C:7]([OH:12])[CH:8]=[C:9]([CH:11]=1)[OH:10])[CH3:4].[CH:18](NC(=O)C)([NH:25][C:26](=[O:28])[CH3:27])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1.P(Cl)(Cl)(Cl)=O.O>C(Cl)Cl>[C:26]([NH:25][CH:18]([C:8]1[C:7]([OH:12])=[CH:6][C:5]([CH:3]([CH:2]([CH3:1])[CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])[CH3:4])=[CH:11][C:9]=1[OH:10])[C:19]1[CH:24]=[CH:23][CH:22]=[CH:21][CH:20]=1)(=[O:28])[CH3:27]

Participants

6

Reactant 4

HCID 962WaterHCID 23346Acetamide, N,N'-benzylidenebis-HCID 24813Phosphorus oxychlorideHCID 2581765-(3-Methyloctan-2-yl)benzene-1,3-diol

Product 1

HCID 54156421HCID 54156421, compoundYield 40%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

A stirred solution-suspension of 11.8 g (0.05 mol) of 5-(3-methyl-2-octyl)-resorcinol (4) (65% dl-erythro and 35% dl-threo) and 10.7 g (0.052 mol) of N,N'-benzylidenebisacetamide (2) in 60 ml of methylene chloride cooled to 2° in an ice bath was treated dropwise with 4.9 ml (0.05 mol) of phosphorus oxychloride over a period of 5 to 10 minutes. The stirring was continued in the melting ice bath. A clear solution formed after 2 to 2.5 hours and precipitation of produce occurred after 3 to 3.5 hours. After being stirred at room temperature overnight, the reaction mixture was treated with water (40 ml) and more methylene chloride (70 ml). After the slight exothermic reaction was complete, the organic layer containing suspended product was separated and washed successively with water (2 × 100 ml), 5% sodium bicarbonate (100 ml), and water (100 ml). Filtration of the organic layer gave 5.00 g of colorless crystalline powder, mp 204-208°. Concentration of the filtrate and cooling gave 2.58 g, mp 196-199°, as a second crop (7.58 g = 40% yield). Concentration to dryness left 10.8 g of an amorphous glassy solid which could not be crystallized. Its pmr spectrum was similar to that of the crystalline fraction, suggesting it consisted of a mixture of stereoisomers. Recrystallization from acetonitrile of a sample of the 7.58 g to constant mp gave pure 2-(α-acetylaminobenzyl)-5-(3-methyl-2-octyl)-resorcinol (6) mp 209°-210° (probably a single stereo-isomer); ir (Nujol) 3400 (νNH or OH), 3200 (broad, ν bonded OH), and 1610 cm-1 (νC=O); pmr (DMSO-d6) δ 9.0 -9.8 (m, 2H, OH), 7.98 (d, 1H, J = 9 Hz, NH), 7.0 - 7.5 (m, 5H, C6H5), 6.64 (d, 1H, J = 9 Hz, Ar2CHNH), 6.18 (s, 2H, C6H2) and 1.92 ppm (s, 3H, CH3CO); m/e (M+) 383.

Workup

  1. temperaturecooled to 2° in an ice bath
  2. customA clear solution formed after 2 to 2.5 hours
  3. customprecipitation
  4. customof produce
  5. customAfter the slight exothermic reaction
  6. additionthe organic layer containing
  7. customwas separated
  8. washwashed successively with water (2 × 100 ml), 5% sodium bicarbonate (100 ml), and water (100 ml)
  9. filtrationFiltration of the organic layer

Sources & evidence

ORD record
ord-5ab0f0b00aa340cd8a5dc98b7a19e5e7
Source dataset
uspto-grants-1978_04
Patent number
US04083868

Reaction notes

Loading…