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Sodium hydride → Ethyl 5-carboethoxy-2-diethylphosphono-2-methylpent-4-enoate

HRID 1706646
Notes
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Reaction equation

HRID 1706646 reaction equation
Br[CH2:2]/[CH:3]=[CH:4]/[C:5]([O:7][CH2:8][CH3:9])=[O:6].[Na].[CH2:11]([O:13][P:14]([CH:19]([CH3:25])[C:20]([O:22][CH2:23][CH3:24])=[O:21])([O:16][CH2:17][CH3:18])=[O:15])[CH3:12].[H-].[Na+]>O1CCOCC1>[C:5]([CH:4]=[CH:3][CH2:2][C:19]([P:14]([O:13][CH2:11][CH3:12])([O:16][CH2:17][CH3:18])=[O:15])([CH3:25])[C:20]([O:22][CH2:23][CH3:24])=[O:21])([O:7][CH2:8][CH3:9])=[O:6]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 4

HCID 24758Sodium hydrideHCID 107155Triethyl 2-phosphonopropionate2×HCID 5360545SodiumHCID 5373944Ethyl (E)-4-bromobut-2-enoate

Product 1

HCID 54104589Ethyl 5-carboethoxy-2-diethylphosphono-2-methylpent-4-enoate

Reagents, catalysts & solvents 1

HCID 31275
1,4-Dioxane
Solvent

Procedure

Ethyl 4-bromocrotonate (19.3 parts) was added dropwise at 25°-30° C. to a solution of the sodium salt of ethyl 2-diethylphosphonopropionate, prepared from 23.8 parts of ethyl 2-diethylphosphonopropionate and 5.3 parts of sodium hydride (50% in oil) in dioxan. The resulting solution was heated at reflux for 18 hr., after which time the sodium bromide was removed by filtration and the solution concentrated in vacuo. The residual oil was distilled to give 12.7 parts of ethyl 5-carboethoxy-2-diethylphosphono-2-methylpent-4-enoate boiling at 158°/0.2 mm. Hydrogenation of 12 parts of this material over 5% palladium on carbon gave 7.2 parts of diethyl 2-diethylphosphono-2-methyladipate boiling at 146°-52° C./0.05 mm; subsequent hydrolysis of 5 parts of this in concentrated hydrochloric acid gave 3.7 parts of 2-methyl-2-phosphonoadipic acid as a glassy solid which had a 31P chemical shift of -24 ppm.

Workup

  1. temperatureThe resulting solution was heated
  2. temperatureat reflux for 18 hr
  3. custom, after which time the sodium bromide was removed by filtration
  4. concentrationthe solution concentrated in vacuo
  5. distillationThe residual oil was distilled

Sources & evidence

ORD record
ord-8d2c18a90ae04ce49eae73308d1877fd
Source dataset
uspto-grants-1980_06
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US04208344

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes