Formaldehyde → HCID 86647798, compound

HRID 84942Notes

Reaction equation

HRID 84942 reaction equation
[C:1]([CH:3]=[CH:4][C:5]1[CH:14]=[CH:13][C:8]([C:9]([O:11][CH3:12])=[O:10])=[CH:7][C:6]=1[C:15]([O:17][CH3:18])=[O:16])#[N:2].[CH3:19][NH:20][CH2:21]C(O)=O.[CH2:25]=O>C1(C)C=CC=CC=1>[C:1]([C@@H:3]1[CH2:25][N:20]([CH3:21])[CH2:19][C@H:4]1[C:5]1[CH:14]=[CH:13][C:8]([C:9]([O:11][CH3:12])=[O:10])=[CH:7][C:6]=1[C:15]([O:17][CH3:18])=[O:16])#[N:2]

Participants

5

Reactant 3

HCID 712Formaldehyde2×HCID 1088Sarcosine2×HCID 66819156Dimethyl 4-(2-cyanovinyl)isophthalate

Product 1

HCID 86647798HCID 86647798, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
125 °C

Procedure

A 100 mL round bottom flask was charged with dimethyl 4-(2-cyanovinyl)isophthalate (380 mg, 1.55 mmol), 2-(methylamino)acetic acid (276 mg, 3.1 mmol), paraformaldehyde (326 mg, 10.85 mmol) and toluene (5 mL). The reaction mixture was heated to 125° C. under nitrogen for 2 hours. Then the solution was transferred to another flask leaving the dark tar behind. 2-(Methylamino)acetic acid (276 mg, 3.1 mmol) and paraformaldehyde (326 mg, 10.85 mmol) were added. The reaction mixture was heated to 125° C. under nitrogen for another 2 hours. Then this was cooled and concentrated and partitioned between saturated NaHCO3(aq.) and ethyl acetate. The organic layer was washed with brine, dried over Na2SO4, concentrated, and purified by flash column chromatography with 80-100% ethyl acetate/hexane to provide the title compound. 1H NMR (300 MHz, DMSO-d6) δ ppm 8.30 (d, J=1.9, 1H), 8.13 (dd, J=2.0, 8.3, 1H), 7.81 (d, J=8.3, 1H), 4.43-4.33 (m, 1H), 3.89 (d, J=5.7, 3H), 3.36 (q, J=8.1, 1H), 3.30 (s, 3H), 3.20-3.10 (m, 1H), 3.02-2.92 (m, 1H), 2.75 (dd, J=6.4, 9.2, 1H), 2.62 (dd, J=5.5, 9.5, 1H), 2.34 (s, 3H); MS (ESI+) m/z 302.9 [M+H]+.

Workup

  1. customThen the solution was transferred to another flask
  2. customleaving the dark tar behind
  3. temperatureThe reaction mixture was heated to 125° C. under nitrogen for another 2 hours
  4. temperatureThen this was cooled
  5. concentrationconcentrated
  6. custompartitioned between saturated NaHCO3(aq.) and ethyl acetate
  7. washThe organic layer was washed with brine
  8. dry with materialdried over Na2SO4
  9. concentrationconcentrated
  10. custompurified by flash column chromatography with 80-100% ethyl acetate/hexane

Sources & evidence

ORD record
ord-f7aec1b384ea4b7da3da3051d5963962
Source dataset
uspto-grants-2014_09
Patent number
US08846951B2

Reaction notes

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