4,4-Azobis(4-cyanovaleric acid) → 4-Cyano-4-[(phenylcarbonothioyl)thio]pentanoic Acid

HRID 1525374Notes

Reaction equation

HRID 1525374 reaction equation
S1C=CC(CC[O:8][C:9](=[O:25])[CH2:10][CH2:11][C:12]([C:23]#[N:24])([S:14][C:15]([C:17]2[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=2)=[S:16])[CH3:13])=C1.N(C(C#N)(C)CCC(O)=O)=NC(C#N)(C)CCC(O)=O.C(SSC(=S)C1C=CC=CC=1)(=S)C1C=CC=CC=1>C(OCC)(=O)C>[C:23]([C:12]([S:14][C:15](=[S:16])[C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1)([CH3:13])[CH2:11][CH2:10][C:9]([OH:25])=[O:8])#[N:24]

Participants

5

Reactant 3

HCID 929384,4-Azobis(4-cyanovaleric acid)HCID 10902862Bis(thiobenzoyl) DisulfideHCID 86634529(Thiophen-3-yl)ethyl-4-cyano-4-(phenylcarbonothioylthio)pentanoate

Product 1

HCID 99217634-Cyano-4-[(phenylcarbonothioyl)thio]pentanoic Acid

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

The synthesis scheme for (thiophen-3-yl)ethyl-4-cyano-4-(phenylcarbonothioylthio)pentanoate is shown in FIG. 15 and is performed as follows. First, the intermediary molecule, 4-Cyano-4-((thiobenzoyl)sulfanyl)pentanoic acid is synthesized by dissolving 4,4′-Azobis(4-cyanovaleric acid) (4.19 g, 0.0149 mol) and bis(thiobenzoyl)disulfide (3.07 g, 0.01 mol) in ethyl acetate (200 mL) in a 500 mL round-bottom flask equipped with a condenser. The mixture is degassed by bubbling with nitrogen and heated to reflux for 20 hours under nitrogen. The reaction is allowed to cool to room temperature, and the solvent is removed in vacuum. The crude product is purified by column chromatography (silica gel) using ethyl acetate:hexanes 2:3 as the eluent. After removal of solvent, the red fraction gives 4-cyano-4-((thiobenzoyl)sulfanyl)-pentanoic acid as a red oil. The product is solidified upon sitting at −20° C. 1H NMR (CDCl3) δ (ppm): 1.93 (s, 3H, CH3); 2.38-2.80 (m, 4H, CH2CH2); 7.42 (m, 2H, m-ArH); 7.56 (t, 1H, J=8 Hz p-ArH); 7.91 (d, 2H, J=7.3 Hz, o-ArH). 13C NMR (CDCl3) δ (ppm): 24.1, 29.5, 32.9, 45.6, 118.4, 126.7, 128.6, 133.1, 144.4, 177.3, 222.1.

Workup

  1. customFirst, the intermediary molecule, 4-Cyano-4-((thiobenzoyl)sulfanyl)pentanoic acid is synthesized
  2. customequipped with a condenser
  3. customThe mixture is degassed
  4. customby bubbling with nitrogen
  5. temperatureheated
  6. temperatureto reflux for 20 hours under nitrogen
  7. customthe solvent is removed in vacuum
  8. customThe crude product is purified by column chromatography (silica gel)
  9. customAfter removal of solvent

Sources & evidence

ORD record
ord-2899f0c61e93438a83259d40bc7ea8c5
Source dataset
uspto-grants-2015_07
Patent number
US09079999B2

Reaction notes

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