Formaldehyde → HCID 13014656, compound

HRID 444595Notes

Reaction equation

HRID 444595 reaction equation
Cl[C:2]([CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][C:9]([O:11][CH2:12][C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1)=[O:10])=[O:3].C=[O:20]>>[CH2:12]([O:11][C:9](=[O:10])[CH2:8][CH2:7][CH2:6][CH2:5][CH2:4][C:2]([OH:20])=[O:3])[C:13]1[CH:18]=[CH:17][CH:16]=[CH:15][CH:14]=1

Participants

3

Reactant 2

HCID 712FormaldehydeHCID 13014657Benzyl 6-chloroformylcaproate

Product 1

HCID 13014656HCID 13014656, compound

Conditions

Temperature
120 °C

Procedure

Pimelic acid monobenzyl ester was prepared according to an adaptation of the method of Hassner et al, Tetrahedron Letters No. 46, 4475 (1970); it boils at 205° C. (1.5 torr). This material was converted to benzyl 6-chloroformylcaproate according to the above methods and 5.25 g of the latter compound was stirred with 0.59 g of paraformaldehyde and several mg of fused zinc chloride and heated to 120° C. in an oil bath. After the paraformaldehyde was consumed (about 11/2 hrs), the mixture was cooled, giving 5.73 g of multi-component product. Purification of 3.85 g of this crude product was achieved on a 180 g (2.9×61 cm) column of Silica Gel 60, prepared in a solvent of toluene/chloroform 9:1. The column was run at the flow rate of 1.8 ml/min. and 20 ml fractions were collected. The column was eluted first with 3 liters of toluene/chloroform 9:1, secondly with 3 liters of a 8.5:1.5 mixture of these solvents and finally with 1 liter of toluene containing 15% of chloroform and 7.5% of ethyl acetate. The various fractions were analyzed and combined where appropriate to produce 1.00 g of an oil identified as benzyl chloromethyl pimelate; ir 1765 and 1735 cm-1 ; pmr δ 7.34, 5.68, 5.11, 2.25-2.50 and 1.1-1.9 ppm.

Workup

  1. customAfter the paraformaldehyde was consumed (about 11/2 hrs)
  2. temperaturethe mixture was cooled
  3. customgiving 5.73 g of multi-component product
  4. customPurification of 3.85 g of this crude product
  5. customprepared in a solvent of toluene/chloroform 9:1
  6. customwere collected
  7. washThe column was eluted first with 3 liters of toluene/chloroform 9:1, secondly with 3 liters of a 8.5:1.5 mixture of these solvents and finally with 1 liter of toluene containing 15% of chloroform and 7.5% of ethyl acetate

Sources & evidence

ORD record
ord-a4e5887dc6ed414aa08b48c18859d410
Source dataset
uspto-grants-1981_04
Patent number
US04264765

Reaction notes

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