Dimethylformamide → HCID 54161734, compound

HRID 2225828Notes

Reaction equation

[CH2:1]([O:3][C:4](=[O:14])[C:5](=[O:13])[C:6]1[CH:11]=[CH:10][C:9]([OH:12])=[CH:8][CH:7]=1)[CH3:2].[H-].[Na+].Br[CH2:18][CH2:19][CH2:20][C:21](=O)[CH2:22][C:23]1[CH:28]=[C:27]([C:29]([CH3:32])([CH3:31])[CH3:30])[C:26]([O:33][CH2:34][O:35][CH2:36][CH2:37][O:38][CH3:39])=[C:25]([C:40]([CH3:43])([CH3:42])[CH3:41])[CH:24]=1.CN(C)C=[O:48]>>[CH2:1]([O:3][C:4](=[O:14])[C:5](=[O:13])[C:6]1[CH:11]=[CH:10][C:9]([O:12][CH2:18][CH2:19][CH2:20][CH2:21][C:22]([C:23]2[CH:24]=[C:25]([C:40]([CH3:42])([CH3:41])[CH3:43])[C:26]([O:33][CH2:34][O:35][CH2:36][CH2:37][O:38][CH3:39])=[C:27]([C:29]([CH3:30])([CH3:32])[CH3:31])[CH:28]=2)=[O:48])=[CH:8][CH:7]=1)[CH3:2]

Participants

Reactant 4

HCID 6228Dimethylformamide2×

HCID 24758Sodium hydride

HCID 11715332Ethyl 2-(4-hydroxyphenyl)-2-oxoacetate

HCID 57062708HCID 57062708, compound

Product 1

HCID 54161734HCID 54161734, compound

Procedure

4-Hydroxy-alpha-oxobenzeneacetic acid ethyl ester (1.44 g) and 55% sodium hydride (0.36 g) in dimethylformamide (30 mL) was stirred for 20 minutes and then treated with 5-bromo-1-[3,5-bis(1,1-dimethylethyl)-4-[(2-methoxyethoxy) methoxy]phenyl]pentanone (3.4 g) in dimethylformamide (6 mL). The mixture was stirred at room temperature for 20 hours and then after an additional 4 hours at 50° C., it was worked up as in Example 20. The residual oil was purified by HPLC (ethyl acetate-toluene; 1:17) to give 2.7 g of 4-[5-[3,5-bis(1,1-dimethylethyl)-4-[(2-methoxyethoxy) methoxy]phenyl]-5-oxopentyloxy]-alpha-oxobenzeneacetic acid ethyl ester as an oil. A solution of the above 4-[5-[3,5-bis(1,1-dimethylethyl)-4-[(2-methoxyethoxy) methoxy]phenyl]-5-oxopentyloxy]-alpha-oxobenzeneacetic acid ethyl ester (2.1 g) was dissolved in dichloromethane (20 mL) containing trifluoroacetic acid (1.1 mL) was stirred at room temperature for 31 hours, then saturated sodium bicarbonate solution was added (25 mL). The separated organic layer was dried (MgSO4) and evaporated and the crude product was purified by HPLC (ethyl acetate-hexane; 4:21). Trituration of the resulting material with hexane afforded 1.4 g of 4-[5-[3,5-bis(1,1-dimethylethyl) -4-hydroxyphenyl]-5-oxopentyloxy]-alpha-oxobenzeneacetic acid ethyl ester, mp 95°-96° C.

Workup

waitafter an additional 4 hours at 50° C.
customThe residual oil was purified by HPLC (ethyl acetate-toluene; 1:17)

Sources & evidence

ORD record: ord-11c0f2d0a90b4762a2cb20f7469ff98a
Source dataset: uspto-grants-1994_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US05344843

Reaction notes

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