Potassium Hydroxide → Methyl 2-[2-(bromomethyl)phenyl]-2-(methoxyimino)acetate

HRID 428791Notes

Reaction equation

HRID 428791 reaction equation
BrCC1C=CC=CC=1/C(=C\OC)/C(OC)=O.[OH-].[Na+].[OH-].[K+].CC1C=CC=CC=1CC([O-])=O.[CH3:32][O:33]/[N:34]=[C:35](\[C:40]1[CH:45]=[CH:44][CH:43]=[CH:42][C:41]=1[CH2:46][Br:47])/[C:36]([O:38][CH3:39])=[O:37].[CH3:48][O:49][N:50]=[C:51]([C:56]1[CH:61]=[CH:60][CH:59]=[CH:58][C:57]=1[CH2:62]Br)[C:52]([O:54][CH3:55])=[O:53].CC1C=CC=CC=1CC(OC)=O>C(C(C)=O)C.CC(C)=O>[CH3:32][O:33][N:34]=[C:35]([C:40]1[CH:45]=[CH:44][CH:43]=[CH:42][C:41]=1[CH2:46][Br:47])[C:36]([O:38][CH3:39])=[O:37].[CH3:48][O:49][N:50]=[C:51]([C:56]1[CH:61]=[CH:60][CH:59]=[CH:58][C:57]=1[CH3:62])[C:52]([O:54][CH3:55])=[O:53]

Participants

11

Reactant 7

HCID 14797Potassium Hydroxide2×HCID 14798Sodium Hydroxide2×HCID 69463472-MethylphenylacetateHCID 7021479Methyl 2-(2-methylphenyl)acetateHCID 9925856(E)-methyl 2-(2-(bromomethyl)phenyl)-3-methoxyacrylate2×HCID 10989774(E)-Methyl 2-(methoxyimino)-2-[2-(bromomethyl)phenyl]acetateHCID 54028047Methyl 2-[2-(bromomethyl)phenyl]-2-(methoxyimino)acetate

Product 2

HCID 54028047Methyl 2-[2-(bromomethyl)phenyl]-2-(methoxyimino)acetateHCID 54500888Methyl 2-(methoxyimino)-2-(2-methylphenyl)acetate

Reagents, catalysts & solvents 2

HCID 180AcetoneSolvent2×HCID 6569Methyl Ethyl KetoneSolvent2×

Procedure

Compounds of formula XV (X is CH) are prepared by alkylation with methyl E-α-(2-bromomethylphenyl)-β-methoxyacrylate (XIV, where A═H, X═CH and L is Br) in the presence of a base, preferably NaOH or KOH, in a solvent, preferably acetone or methyl ethyl ketone. Methyl E-α-(2-bromomethylphenyl)-β-methoxyacrylate, as a single E isomer, can be prepared in two steps from 2-methylphenylacetate as described previously in U.S. Pat. No. 4,914,128, columns 3-4. Compounds of formula XVI (X═N) are prepared by the reaction with methyl E-2-(bromomethyl)phenylglyoxylate O-methyloxime (XIV, where A═H, X═N and L is Br) in the presence of a base, preferably NaOH or KOH, in a solvent, preferably acetone or methyl ethyl ketone. Methyl 2-(bromomethyl)phenylglyoxylate O-methyloxime can be prepared as described in U.S. Pat. No. 4,999,042, columns 17-18 and 5,157,144, columns 17-18. Methyl 2-(bromomethyl)phenylglyoxylate O-methyl-oxime is prepared from methyl 2-methylphenyl-acetate by treatment with an alkyl nitrite under basic conditions to provide after methylation, methyl 2-methyl-phenyl-glyoxalate O-methyl oxime which can also be prepared from methyl 2-methyl-phenylglyoxalate by treatment with 2-hydroxylamine hydrochloride and methylation or by treatment with methoxylamine hydrochloride.

Sources & evidence

ORD record
ord-f3b1130c1da140e48a92713b93dbc569
Source dataset
uspto-grants-2001_11
Patent number
US06313339B1

Reaction notes

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