Hydrochloric Acid → HCID 178441218, compound

HRID 2168573Notes

Reaction equation

HRID 2168573 reaction equation
C(C1C=CC(CN)=CC=1)=C.[C:11]1([P:17]([C:47]2[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=2)[C-:18]2[CH:22]=[C:21]([C:23]([CH3:33])([CH2:25]C[CH:27]3OCCC[O:28]3)[CH3:24])[CH:20]=[C:19]2[P:34]([C:41]2[CH:46]=[CH:45][CH:44]=[CH:43][CH:42]=2)[C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[C:53]([C:57]1[CH:58]=[C:59]([P:75]([C:82]2[CH:87]=[CH:86][CH:85]=[CH:84][CH:83]=2)[C:76]2[CH:81]=[CH:80][CH:79]=[CH:78][CH:77]=2)[C-:60]([P:62]([C:69]2[CH:74]=[CH:73][CH:72]=[CH:71][CH:70]=2)[C:63]2[CH:68]=[CH:67][CH:66]=[CH:65][CH:64]=2)[CH:61]=1)([CH3:56])([CH3:55])[CH3:54].[Fe+2:88].Cl>C1COCC1>[C:63]1([P:62]([C:69]2[CH:74]=[CH:73][CH:72]=[CH:71][CH:70]=2)[C-:60]2[CH:61]=[C:57]([C:53]([CH3:56])([CH2:54][CH:27]=[O:28])[CH3:55])[CH:58]=[C:59]2[P:75]([C:76]2[CH:77]=[CH:78][CH:79]=[CH:80][CH:81]=2)[C:82]2[CH:87]=[CH:86][CH:85]=[CH:84][CH:83]=2)[CH:68]=[CH:67][CH:66]=[CH:65][CH:64]=1.[C:23]([C:21]1[CH:20]=[C:19]([P:34]([C:35]2[CH:40]=[CH:39][CH:38]=[CH:37][CH:36]=2)[C:41]2[CH:42]=[CH:43][CH:44]=[CH:45][CH:46]=2)[C-:18]([P:17]([C:47]2[CH:52]=[CH:51][CH:50]=[CH:49][CH:48]=2)[C:11]2[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=2)[CH:22]=1)([CH3:33])([CH3:24])[CH3:25].[Fe+2:88]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 110734664-VinylbenzylamineHCID 178441217HCID 178441217, compound

Product 1

HCID 178441218HCID 178441218, compoundYield 96.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

For the deprotection leading to the actual compound of formula (9), with E=(CH2)3 and GF=4-vinyl-benzylamine, a solution of 1,1′,2,2′-tetrakis(diphenyl-phosphino)-4-[4-(1,3-dioxan-2-yl)-2-methylbut-2-yl]-4′-tert-butylferrocene (0.1 g, 88 μmol) in 20 ml of THF is admixed with 5 ml of 2N hydrochloric acid solution. The solution is placed under microwave radiation (125 W) according to the following program: temperature rise 10° C./min to 120° C., then plateau at 120° C. for 10 min. After cooling, the reaction mixture is concentrated under vacuum, diluted with 20 ml of water, and extracted with 2 times 25 ml of CH2Cl2. The organic phase is dried over MgSO4 and concentrated under reduced pressure. The crude product obtained is purified by chromatography on silica gel (eluent AcOEt/heptane 1:4) to give 90 mg (ρ=90%) of 1,1′,2,2′-tetrakis(diphenylphosphino)-4-(4-oxo-2-methylbut-2-yl)-4′-tert-butylferrocene in the form of a red powder, for which the 31P NMR spectrum preserves, as expected, the ABCD spin system appearance, with slightly modified chemical shifts.

Workup

  1. temperatureAfter cooling
  2. concentrationthe reaction mixture is concentrated under vacuum
  3. additiondiluted with 20 ml of water
  4. extractionextracted with 2 times 25 ml of CH2Cl2
  5. dry with materialThe organic phase is dried over MgSO4
  6. concentrationconcentrated under reduced pressure
  7. customThe crude product obtained
  8. customis purified by chromatography on silica gel (eluent AcOEt/heptane 1:4)

Sources & evidence

ORD record
ord-47dd5bbfecb946b5826194942e8002d6
Source dataset
uspto-grants-2015_06
Patent number
US09045511B2

Reaction notes

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