HCID 9959542, compound → HCID 11050014, compound

HRID 1508368Notes

Reaction equation

HRID 1508368 reaction equation
[S:1]([O-:5])([OH:4])(=[O:3])=[O:2].[CH3:6]/[C:7](/[CH:29]=[CH:30]/[C:31]1[C:36]([CH3:38])([CH3:37])[CH2:35][CH2:34][CH2:33][C:32]=1[CH3:39])=[CH:8]\[CH2:9][P+:10]([C:23]1[CH:28]=[CH:27][CH:26]=[CH:25][CH:24]=1)([C:17]1[CH:22]=[CH:21][CH:20]=[CH:19][CH:18]=1)[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.C[O-].[Na+]>CO>[CH3:6]/[C:7](/[CH:29]=[CH:30]/[C:31]1[C:36]([CH3:38])([CH3:37])[CH2:35][CH2:34][CH2:33][C:32]=1[CH3:39])=[CH:8]/[CH2:9][P+:10]([C:17]1[CH:18]=[CH:19][CH:20]=[CH:21][CH:22]=1)([C:23]1[CH:24]=[CH:25][CH:26]=[CH:27][CH:28]=1)[C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.[S:1]([O-:5])([OH:4])(=[O:3])=[O:2]

Participants

4

Reactant 2

HCID 9959542HCID 9959542, compoundHCID 10942334Sodium Methoxide

Product 1

HCID 11050014HCID 11050014, compoundYield 20%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Conditions

Temperature
145 °C

Procedure

A 4000 ml round-bottom flask is initially charged with 2535 g (1.67 mol) of a 37.2% by weight solution of [(2E,4E)-3-methyl-5-(2,6,6-trimethylcyclohexen-1-yl)penta-2,4-dienyl]triphenylphosphonium hydrogensulfate in methanol under nitrogen, which is alkalized by addition of 111.30 g (0.618 mol) of a 30% by weight sodium methoxide solution in methanol, and the precipitated sodium sulfate is filtered off. The filtrate is pumped through a flow reactor heated to 145° C. with an exactly fixed residence time of 25 min. Subsequently, the solvent is distilled off, the residue is taken up in isopropanol and acidified with sulfuric acid to a pH of 0.3, and the unisomerized [(2E,4E)-3-methyl-5-(2,6,6-trimethylcyclohexen-1-yl)penta-2,4-dienyl]triphenylphosphonium salt of the general formula 2 is crystallized by adding 823 g of heptane and cooling to −10° C. After the crystals have been filtered off, 1648 g of an 11.2% by weight solution of [(2Z,4E)-3-methyl-5-(2,6,6-trimethylcyclohexen-1-yl)penta-2,4-dienyl]triphenylphosphonium-hydrogensulfate (0.327 mol) are obtained in a purity of 95% and a yield of 20%.

Workup

  1. filtrationthe precipitated sodium sulfate is filtered off
  2. customThe filtrate is pumped through a flow reactor
  3. distillationSubsequently, the solvent is distilled off
  4. customthe unisomerized [(2E,4E)-3-methyl-5-(2,6,6-trimethylcyclohexen-1-yl)penta-2,4-dienyl]triphenylphosphonium salt of the general formula 2 is crystallized
  5. additionby adding 823 g of heptane
  6. temperaturecooling to −10° C
  7. filtrationAfter the crystals have been filtered off

Sources & evidence

ORD record
ord-fbe704e8a316449486aa4f7d9bbb9c33
Source dataset
uspto-grants-2015_12
Patent number
US09221854B2

Reaction notes

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