Acrylonitrile → 2-Methyl-3-phenylpyridine

HRID 485697Notes

Reaction equation

HRID 485697 reaction equation
[N:1]1[C:2]2[C:3](=[C:7]3[C:12]([CH:13]=2)=[CH:11][CH:10]=[CH:9][C:8]3=O)[CH:4]=[CH:5][CH:6]=1.N1C2C(=O)C3C(=CC=CC=3)C=2C=CC=1.C(#N)C=C.C(CCC(C1C=CC=CC=1)C(=O)C)#N.C(CCC(C1C=CC(F)=CC=1)C(=O)C)#N.CC(=O)CCC.CC1C(C2C=CC=CC=2)CCCN1.CC1C(C2C=CC(F)=CC=2)CCCN1>>[CH3:13][C:2]1[C:3]([C:7]2[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=2)=[CH:4][CH:5]=[CH:6][N:1]=1

Participants

9

Reactant 8

HCID 7855AcrylonitrileHCID 78952-PentanoneHCID 426139H-Indeno(2,1-b)pyridin-9-oneHCID 125014315-Cyano-3-phenyl-2-pentanoneHCID 125014322-Methyl-3-phenylpiperidine2×HCID 198746072-Methyl-3-(4'-fluorophenyl)piperidineHCID 198746155-Cyano-3-(4'-fluorophenyl)-2-pentanoneHCID 198746615H-indeno[2,1-b]pyridine-5-one

Product 1

HCID 5978392-Methyl-3-phenylpyridine

Procedure

The ketone, from the above, is reduced to a method cited in Method VIII or in general the Wolff-Kishner reduction to yield corresponding 9H-indeno[2,1-b]pyridine which is then derivatized in accordance with Methods II, III and IV to yield spiro-thiazolidinedione, spiro-succinimide. Alternatively, 5H-indeno[2,1-b]pyridine-5-one(also called 1-azafluoren-9-one) and 5 to 8 position fluoro or chloro derivatives are prepared according to a general procedure of Urbina, Synthetic Comm., 9, 245(1979). Where to a substituted or unsubstituted 1-phenyl-2-propanone (e.g., 1-(4'-fluorophenyl)-2-propanone) is added acrylonitrile producing a corresponding 5 -cyano-3-phenyl-2-pentanone, e.g., 5-cyano-3-(4'-fluorophenyl)-2-pentanone. The pentanone product is hydrogenated and cyclized to the corresponding 2-methyl-3-phenylpiperidine, e.g., 2-methyl-3-(4'-fluorophenyl)piperidine. Aromatization of the 2-methyl-3-phenyl piperidine is carried out in vapor phase with catalyst K-16 (Prostakon, Mathew and Kurisher, Khim-Geterotsikl. Socd., 876 (1970) at 380° to 420° C. to yield the corresponding 2-methyl-3-phenylpyridine. Alternatively, aromatization can be achieved with Pd/C. Dehydrocyclization of the methyl-3-phenylpyridine at 500° to 550° C. over K-16 will produce the appropriate 1-azafluorene, e.g., 7-fluoro-1-azafluorene. The 9H-indeno[2,1-b]pyridine and its derivatives (e.g., 7-fluoro-9H-indeno[2,1-b]pyridine) are converted in accordance with Method II, III and IV into spiro-thiazolidinedione, spiro-oxazolidinedione and spiro-succinimide derivatives. The 9Hindeno[2,1-b]pyridine is oxidized according to general procedures cited in Method VII or potassium permanganate (Urbina, ibid). The resulting ketone, e.g., 7-fluoro-9H-indeno[2,1-b]pyridin-5-one, is derivatized in accordance with Method I to yield the spiro-hydantoin derivative, such as spiro-(7-fluoro-9H-indeno[2,1-b]pyridin-9,4'-imidazolidine)-2',5'-dione.

Sources & evidence

ORD record
ord-3014d53e01f549a2a66abf566229eb69
Source dataset
uspto-grants-1985_08
Patent number
US04537892

Reaction notes

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