18-Crown-6 → HCID 67257577, compound

HRID 1752172Notes

Reaction equation

HRID 1752172 reaction equation
[CH3:1][CH:2]([CH2:13][CH2:14][C:15]1[C:20]([CH3:22])([CH3:21])[CH2:19][CH2:18][CH2:17][C:16]=1[CH3:23])[CH:3]=[C:4]([C:9]([O:11]C)=[O:10])[C:5]([O:7]C)=[O:6].C1OCCOCCOCCOCCOCCOC1>CC[N+](CC1C=CC=CC=1)(CC)CC.[Cl-].[OH-].[Na+]>[CH3:1][CH:2]([CH2:13][CH2:14][C:15]1[C:20]([CH3:22])([CH3:21])[CH2:19][CH2:18][CH2:17][C:16]=1[CH3:23])[CH:3]=[C:4]([C:9]([OH:11])=[O:10])[C:5]([OH:7])=[O:6]

Participants

5

Reactant 2

HCID 2855718-Crown-6HCID 24938928Propanedioic acid, 2-[2-methyl-4-(2,6,6-trimethyl-1-cyclohexen-1-yl)butylidene]-, 1,3-dimethyl ester

Product 1

HCID 67257577HCID 67257577, compoundYield 87%

Reagents, catalysts & solvents 2

HCID 66133Benzyl triethylammonium chlorideCatalystHCID 14798Sodium HydroxideSolvent

Conditions

Temperature
25 °C

Procedure

Dimethyl malonate 3a (10 g, 28 mmol), TEBAC (0.33 g, 1.4 mmol) (or 18-Crown 6) and 1N NaOH (120 ml) are stirred at 100° C. for 3 days. Cooled to 25° C. the mixture is extracted with tert-butyl methyl ether and the organic phase, which contains aldehyde 5, is discarded. 100 ml 2 N HCl are added to the aqueous phase, which is extracted with tert-butyl methyl ether. The organic phase is washed with water, dried over MgSO4, filtered and evaporated to give 7.15 g of crude bis-acid 1c (87%). Analytical data: 1H-NMR (400 MHz, CDCl3): δ 0.96 (s, 6 H), 1.13 (d, 3 H), 1.35-1.6 (6 H), 1.56 (s, 3 H), 1.85-2.1 (4 H), 3.5 (m, 1 H), 7.6 (d, 1 H) ppm. 13C-NMR (400 MHz, CDCl3): δ 19.1 (q), 19.4 (t), 19.8 (q), 26.5 (t), 28.5 (2 q), 32.7 (t), 34.8 (s), 35.6 (d), 36.9 (t), 39.7 (t), 120.0 (s), 127.3 (s), 136.8 (s), 168.3 (s), 169.2 (d), 1669.7 (s). MS (DIP, EI): m/z (%) 294 (M+, 67), 279 (8), 276 (14), 261 (18), 258 (17), 243 (100), 233 (12), 215 (22), 190 (16), 187 (15), 175 (32), 151 (14), 144 (44), 135 (32), 126 (14), 123 (31), 121 (16), 107 (9), 95 (9). IR (film): 2969 (m), 2929 (m), 2867 (m), 1701 (s), 1367 (m), 1262 (m), 1237 (m), 1199 (s), 1172 (m), 1067 (m), 842 (m), 761 (m).

Workup

  1. extractionis extracted with tert-butyl methyl ether
  2. addition100 ml 2 N HCl are added to the aqueous phase, which
  3. extractionis extracted with tert-butyl methyl ether
  4. washThe organic phase is washed with water
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. customevaporated

Sources & evidence

ORD record
ord-14b2d658bd574e5282443cf277dec48a
Source dataset
uspto-grants-2015_10
Patent number
US09163000B2

Reaction notes

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