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1-Pentyne, 5-chloro- → 2-Ethoxy-4-p-tolyl-6-chloropropyl-1,2-oxaphosphorin 2-oxide

HRID 1499003
Notes
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Reaction equation

HRID 1499003 reaction equation
CC(P(C(C)(C)C)C1C(C2C=CC=CC=2)=CC=CC=1)(C)C.[C:22]1([CH3:36])[CH:27]=[CH:26][C:25]([C:28]#[C:29][P:30](=[O:35])([OH:34])[O:31][CH2:32][CH3:33])=[CH:24][CH:23]=1.[Cl:37][CH2:38][CH2:39][CH2:40][C:41]#[CH:42]>[Au].ClC(Cl)C>[CH2:32]([O:31][P:30]1(=[O:34])[CH:29]=[C:28]([C:25]2[CH:24]=[CH:23][C:22]([CH3:36])=[CH:27][CH:26]=2)[CH:42]=[C:41]([CH2:40][CH2:39][CH2:38][Cl:37])[O:35]1)[CH3:33]
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 3

HCID 843081-Pentyne, 5-chloro-HCID 27342152-(Di-tert-butylphosphino)biphenylHCID 71546601Ethyl hydrogen p-tolylethynylphosphonate

Product 1

HCID 715466022-Ethoxy-4-p-tolyl-6-chloropropyl-1,2-oxaphosphorin 2-oxideYield 70%

Reagents, catalysts & solvents 2

HCID 23985GoldCatalyst
HCID 6365
1,1-Dichloroethane
Solvent
2×

Procedure

Method 2—A gold (Ag(I)) catalyst {[Au(JohnPhos)NCCH3]+SbF6—} [JohnPhos:(2-biphenyl)di-tent-butylphosphine] (11.3 mg, 0.015 mmol) was put into a reaction container, and dichloroethane (0.4 mL) was put thereinto. After stirring at room temperature for 5 minutes, ethyl hydrogen p-tolylethynylphosphonate (67.3 mg, 0.3 mmol) diluted with 0.5 mL of dichloroethane was added thereto, and finally, 5-chloropent-1-yne (61.5 mg, 0.6 mmol) was put thereinto. Then, when all of the starting materials disappeared in the TLC, the reaction was allowed to be completed. After the solvent was removed under low atmospheric pressure, the product was separated by chromatography to obtain 2-ethoxy-4-p-tolyl-6-chloropropyl-1,2-oxaphosphorin 2-oxide (68.5 mg, 70%) which is a title compound.

Workup

  1. additionwas added
  2. customAfter the solvent was removed under low atmospheric pressure
  3. customthe product was separated by chromatography

Sources & evidence

ORD record
ord-5283302e5160461c89f6dc4f168bfd04
Source dataset
uspto-grants-2015_12
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US09200019B2

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes