Tris(Hydroxymethyl)Phosphine → Dimethyl-9-octadecenedioate

HRID 2167346Notes

Reaction equation

HRID 2167346 reaction equation
[C:1]([O:12][CH3:13])(=[O:11])[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH:9]=[CH2:10].[C:14]([O:27][CH3:28])(=[O:26])[CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21]C=CCC.OCP(CO)CO>C1(C)C=CC=CC=1>[C:14]([O:27][CH3:28])(=[O:26])[CH2:15][CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][CH2:21][CH:10]=[CH:9][CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][CH2:3][CH2:2][C:1]([O:12][CH3:13])=[O:11]

Participants

5

Reactant 3

HCID 76001Tris(Hydroxymethyl)Phosphine2×HCID 534675Methyl 9-dodecenoate2×HCID 1778877Methyl 9-decenoate2×

Product 1

HCID 53875709Dimethyl-9-octadecenedioate

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
60 °C

Procedure

A dibasic ester composition is produced in accordance with the exemplary procedure below, including a cross-metathesis reaction between methyl 9-decenoate (9-decenoic acid methyl ester, 9-DAME) and methyl 9-dodecenoate (9-dodecenoic acid methyl ester, 9-DDAME). A 1.0:1.0 mole ratio mixture of 9-DAME and 9-DDAME (332 g) is charged to a 1 L round bottom flask and heated to 60° C. Pressure is adjusted to 100 mg Hg with ChemGlass diaphragm vacuum pump model CG-4812-30/and J-Kem Scientific Digital Vacuum Regulator Model 200 and stirring is initiated with a magnetic stir bar. After the system stabilizes at desired conditions, 80 ppm of C-827 (as toluene solution) is added (t=0 min). At approximately 15-20 min, the reaction starts bubbling vigorously and the pressure rises to approximately 500 mm Hg. Pressure restabilizes at 100 mm Hg after approximately 5-10 more minutes. At 180 min, an additional 40 ppm of the catalyst C-827 (as toluene solution) is added. Subsequently, the catalyst is deactivated with 25 equivalents tris hydroxymethyl phosphine (THMP) to C-827 at 80° C. for 120 min, THMP. The catalyst is then removed by water extraction (5:1 oil to water). The composition is dried with MgSO4. Then, light FAME stripping is conducted at 1 mm Hg and approximately 100° C. The products from this reaction include a large fraction of 18:1 dibasic ester.

Workup

  1. additionis charged to a 1 L round bottom flask
  2. customis initiated with a magnetic stir bar
  3. additionis added (t=0 min)
  4. customthe reaction starts bubbling vigorously
  5. waitAt 180 min
  6. additionan additional 40 ppm of the catalyst C-827 (as toluene solution) is added
  7. customThe catalyst is then removed by water extraction (5:1 oil to water)
  8. dry with materialThe composition is dried with MgSO4
  9. customis conducted at 1 mm Hg and approximately 100° C

Sources & evidence

ORD record
ord-852827d118b240bd88fa0afa4f5d769e
Source dataset
uspto-grants-2015_06
Patent number
US09045447B2

Reaction notes

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