o-Bis(bromomethyl)benzene → HCID 21319341, compound
Reaction equation
O=[C:2]([CH2:8][C:9](OC)=O)[CH2:3][C:4](OC)=O.BrC[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][C:16]=1CBr.C[O-].[Na+]>C1COCC1.CO>[CH2:2]1[C:8]2=[CH:9][CH:19]=[CH:20][CH:15]=[CH:16][C:17]2=[CH:18][CH:4]=[CH:3]1Participants
Reactant 3
Product 1
Reagents, catalysts & solvents 1
Procedure
Accordingly, compounds of formula (Ca) are prepared, as set forth above in REACTION SCHEME 2B, by first combining a pentane-3-dioate, e.g. dimethyl 3-oxopentanedioate shown, with a 1,2-bismethyl aromatic having a suitable leaving group on each methyl group, e.g., 1,2-bis(bromomethyl)benzene, in a mixed protic/aprotic solvent medium, e.g., THF-MeOH, and a metal alkoxide, e.g., sodium methoxide. The metal alkoxide can be added as such or made in situ via careful addition (e.g., at low temperature) of the appropriate metal to at least the protic solvent, preferably prior to combination with the remaining reactants. The intermediate benzo[7]annulene product so formed can be optionally isolated and may contain one or two carboxy ester groups depending on the reaction conditions, e.g., methyl 7-oxo-6,7,8,9-tetrahydro-5H-benzo[7]annulene-6,8-dicarboxylate, as shown above. The intermediate, dimethyl 7-oxo-6,7,8,9-tetrahydro-5H-benzo[7]annulene-6,8-dicarboxylate, is subjected to basic hydrolysis (saponification) conditions followed by acidification to give compounds of formula (Ca).
Workup
- customAccordingly, compounds of formula (Ca) are prepared
- customas set forth above in REACTION SCHEME 2B
- additionmade in situ via careful addition (e.g., at low temperature) of the appropriate metal to at least the protic solvent
Sources & evidence
- ORD record
- ord-104c192b95e2490fb66022515df18927
- Source dataset
- uspto-grants-2014_06
- Patent number
- US08741898B2
Reaction notes
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