Benzaldehyde → Homophthalic anhydride

HRID 363847Notes

Reaction equation

HRID 363847 reaction equation
[CH:1](=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C[O:10][CH:11]([O:14]C)OC.[CH3:16]N(C=O)C>C(Cl)(Cl)Cl.NCC(O)=O.C(N(CC)CC)C>[C:11]1(=[O:14])[O:10][C:1](=[O:8])[C:2]2=[CH:7][CH:6]=[CH:5][CH:4]=[C:3]2[CH2:16]1

Participants

7

Reactant 3

HCID 240BenzaldehydeHCID 6228DimethylformamideHCID 9005Trimethyl orthoformate

Product 1

HCID 12801Homophthalic anhydride

Reagents, catalysts & solvents 3

HCID 750GlycineCatalystHCID 8471TriethylamineCatalystHCID 6212ChloroformSolvent

Procedure

Placed in a 20 ml bottle were one of the small (0.241 g of mixed amino acid resin) tea-bags and one of the control (18 micromoles of glycine) tea-bags. The two tea-bags were treated with a solution of benzaldehyde (0.508 ml, 5 mmoles) and anhydrous trimethylorthoformate (1.094 ml, 10 mmoles) in anhydrous DMF (9 ml). After shaking for 3 hrs the packet was washed with anhydrous DMF (3×8 ml). A solution of homophthalic anhydride (801 mg, 5 mmoles) and triethylamine (0.044 ml, 0.3 mmoles) was prepared in chloroform (10 ml) and added to the tea-bag. After shaking at room temperature for 15.5 hrs the packet was washed with DMF (6×30 ml) and DCM (4×30 ml) and dried at room temperature. The remaining 37 tea-bags of mixed resin were each paired with one glycine control tea-bag and reacted as above in 37 separate reactions with the following aldehydes: 1, 4-benzodioxan-6-carboxaldehyde, 1-methylindole-3-carboxaldehyde, 2,3-difluorobenzaldehyde, 2-bromobenzaldehyde, 2-chloro-5-nitrobenzaldehyde, 2-furaldehyde, 2-imidazolecarboxaldehyde, 2-naphthaldehyde, 2-pyridinecarboxaldehyde, 2-thiophenecarboxaldehyde, 3,4-dichlorobenzaldehyde, 3,5-bis(trifluoromethyl)benzaldehyde, 3,5-dihydroxybenzaldehyde, 3,5-dimethoxybenzaldehyde, 3,5-dimethyl-4-hydroxybenzaldehyde, 3-(4-methoxyphenoxy)benzaldehyde, 3-furaldehyde, 3-hydroxybenzaldehyde, 3-methyl-4-methoxybenzaldehyde, 3-methylbenzaldehyde, 3-nitrobenzaldehyde, 3-pyridinecarboxaldehyde, 3-thiophenecarboxaldehyde, 4-(3-dimethylaminopropoxy)benzaldehyde, 4-(dimethylamino)benzaldehyde, 4-(methylthio)benzaldehyde, 4-(trifluoromethyl)benzaldehyde, 4-biphenylcarboxaldehyde, 4-bromo-2-thiophenecarboxaldehyde, 4-cyanobenzaldehyde, 4-methoxy-1-naphthaldehyde, 4-nitrobenzaldehyde, 4-pyridinecarboxaldehyde,5-(hydroxymethyl)-2-furaldehyde, 5-bromo-4-hydroxy-3-methoxybenzaldehyde, 5-nitro-2-furaldehyde and 6-methyl-2-pyridine-carboxaldehyde. The large tea-bag containing 1.204 g (900 micromoles total of mixed amino acids) of resin was reacted with 3,5-dimethoxybenzaldehyde in the same manner, but on a five times larger scale of all reagents and solvents and with no control tea-bag.

Workup

  1. washwas washed with anhydrous DMF (3×8 ml)
  2. additionadded to the tea-bag
  3. stirringAfter shaking at room temperature for 15.5 hrs the packet
  4. washwas washed with DMF (6×30 ml) and DCM (4×30 ml)
  5. customdried at room temperature
  6. customeach paired with one glycine control tea-bag and reacted as above in 37
  7. customseparate reactions with the following aldehydes
  8. additionThe large tea-bag containing 1.204 g (900 micromoles total of mixed amino acids) of resin
  9. customwas reacted with 3,5-dimethoxybenzaldehyde in the same manner

Sources & evidence

ORD record
ord-c51a9cb50b57489797f150d91e5679e5
Source dataset
uspto-grants-1999_02
Patent number
US05874443

Reaction notes

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