Acetonitrile → trans 3'-Methoxystilbene-2,5-dicarboxylic acid

HRID 441670ノート

反応式

HRID 441670 の反応式
[Br-].[C:2]([C:6]1[CH:31]=[CH:30][C:29]([C:32]([O:34]C)=[O:33])=[CH:28][C:7]=1[CH2:8][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([O:4]C)=[O:3].[CH3:36][O:37][C:38]1[CH:39]=[C:40]([CH:43]=[CH:44][CH:45]=1)[CH:41]=O.C(#N)C.C1(C2CCCCCCCC=2)CCCCCCNN=1>O>[CH3:36][O:37][C:38]1[CH:39]=[C:40]([CH:43]=[CH:44][CH:45]=1)/[CH:41]=[CH:8]/[C:7]1[C:6]([C:2]([OH:4])=[O:3])=[CH:31][CH:30]=[C:29]([C:32]([OH:34])=[O:33])[CH:28]=1

参加物

6

反応物 4

HCID 6342AcetonitrileHCID 115693-MethoxybenzaldehydeHCID 66586414DiazabicylononeneHCID 867349972,5-Bis(carbomethoxy)benzyltriphenylphosphonium bromide

生成物 1

HCID 21419698trans 3'-Methoxystilbene-2,5-dicarboxylic acid

試薬・触媒・溶媒 1

HCID 962Water溶媒

実験手順

20 G. of 2,5-bis(carbomethoxy)benzyltriphenylphosphonium bromide and 7.65 g. of m-methoxybenzaldehyde were added to 100 ml of acetonitrile and 22 ml of diazabicyclononene was added. After 16 hours the mixture was added to water and extracted with ethyl acetate. The extract was washed, dried and evaporated. The residue was refluxed for 1 hour in 250 ml of methanol and 250 ml of water containing 10 g. of potassium hydroxide. The solution was cooled and extracted with chloroform. The aqueous layer was acidified with dilute hydrochloric acid and extracted with ethyl acetate. The extract was washed, dried and evaporated to afford cis and trans 3'-methoxystilbene-2,5-dicarboxylic acid. 7.8 G. of this compound was hydrogenated for 11/2 hours in 800 ml of ethanol containing 1.5 g. of 5% palladium on carbon catalyst. The solution was filtered and evaporated to give 2-(m-methoxyphenethyl)-benzene-1,4-dicarboxylic acid which was cyclized according to the procedure set forth in Example I, A to afford 2-carboxy-8-methoxy-10,11-dihydro-5-oxo-5H-dibenzo[a,d]cycloheptene having a m.p. of 220°-222° C. Similarly, other 8-substituted compounds of this invention may be obtained by reacting 2,5-bis(carbomethoxy) benzyltriphenylphosphonium bromide with a m-substituted benzaldehyde having a halogen such as fluoro, chloro or bromo, a lower alkyl of 1-4 carbons, or a lower alkoxy such as ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, n-pentyloxy, n-hexyloxy and the like. By reacting an o-substituted benzaldehyde or a p-substituted benzaldehyde with 2,5-bis(carbomethoxy) benzyltriphenylphosphonium bromide a 2-carboxy-9-substituted-10,11-dihydro-5-oxo-5H-dibenzo[a,d]cycloheptene or a 2-carboxy-7-substituted 10,11-dihydro-5-oxo-5 H-dibenzo[a,d]cycloheptene is obtained, respectively. For example 2-carboxy-7-methyl-10,11-dihydro-5-oxo-5H-dibenzo[a,d]cycloheptene having a m.p of 235° C. was obtained from p-methylbenzaldehyde; 2-carboxy-8-methyl-10,11-dihydro-5-oxo-5H-dibenzo[a,d]cycloheptene having a m.p. of 196°-197° C. was obtained from m-methylbenzaldehyde; and 2-carboxy-9-methyl-10,11-dihydro-5-oxo-5H-dibenzo[a,d]cycloheptene having a m.p. of 232°-234° C. was obtained from o-methylbenzaldehyde.

後処理

  1. additionwas added
  2. extractionextracted with ethyl acetate
  3. washThe extract was washed
  4. customdried
  5. customevaporated
  6. temperatureThe residue was refluxed for 1 hour in 250 ml of methanol
  7. temperatureThe solution was cooled
  8. extractionextracted with chloroform
  9. extractionextracted with ethyl acetate
  10. washThe extract was washed
  11. customdried
  12. customevaporated

出典と根拠

ORDレコード
ord-e480721f387141d7ae1c999e493db1f2
出典データセット
uspto-grants-1977_08
特許番号
US04041173

反応ノート

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