Nitro alkene derivativesH.B. Hass, A.G. Susie, R.L. HeiderJ.Org. Chem. Vol 15, pp. 8-14 (1950)
(
https://www.thevespiary.org/rhodium/Rhodium/pdf/nitrostyrenes.fe-hcl.pdf)
1-Phenyl-2-nitropropeneOne mol each of benzaldehyde and nitroethane, 5 ml n-butylamine and 100 ml EtOH were refluxed for 8 hours in a 1000 ml rb-flask. When the contents were cooled and stirred a heavy yellow crystalline mass formed immediately. After recrystallization from absolute EtOH the product weighed 105 g (conversion 64% of theory, yield 86,5%) with a m.p. of 65°C.
1-Phenyl-2-propanoneOne-tenth of a mole of nitroalkene, 0,72 gram atom (40 g) of 40 mesh cast iron turnings, 75 - 100 ml of distilled water and 0,1 g of ferric chloride were placed in a 500 ml rb-three-neck flask equipped with a graduated dropping funnel, a mercury-seal stirrer and a reflux condenser. Fifteen ml of conc. HCl was added dropwise over 5-6 hours and the temperature of the surrounding oil-bath maintained between 85 - 95°C. The mixture was then basified with 25% aq NaOH and steam distilled. the distillate was extracted several times with ether, the ether distilled and the residue rectified through a Podbielniak column at reduced pressure.
--------Molar ratio--------ml/mole alkene--------Product--------
--Fe/alkene--HCl/alkene----Water--Solvent------P2P--P2p oxime---
---2---------0-------------500-----0----------0%------ 20,1%-----
---2---------0,06----------500-----0----------5,2%-----49,0%-----
---2---------0-------------500-----0----------0%-------0%--------
---2---------0,1-----------500-----0----------11,3%----32,5%-----
---2---------0,232---------500-----0----------24,6%----27,4%-----
---2---------0,464---------500-----0----------36,5%----23,1%-----
---2---------0-------------500-----0----------3,7%-----23,8%-----
---2---------0,06----------500-----0----------3,7%-----45,0%-----
---2---------0.06------------0---500(a)-------0%-------0%--------
---1---------0,06----------500-----0----------trace----34,6%-----
---2---------0,06----------250---500(a)-------10,5%----62,6%-----
---2---------0,06----------250---500(b)-------0%-------0%--------
---2---------0,06----------250---250(a)-------10,7%----45,6%-----
---2---------0,06----------250---250(b)-------0%-------0%--------
---1---------0,06----------250---250(b)-------0%-------0%--------
---2---------0,06----------250---250(c)-------9,9%-----64,2%-----
---2---------0,06----------250---500(c)-------9,7%-----63,0%-----
---2---------1,392---------500-----0----------41,1%----20,2%-----
---2---------1,74----------500-----0----------56,0%----13,4%-----
---2---------1,74---------1000---500(c)-------41,0%----30,2%-----
---2---------1,74---------1000---500(b)-------18,7%----40,3%-----
---7,15------1,74----------750-----0----------75%------0%--------
---7,15------1,97----------670-----0----------77%------0%--------
---2,5-------2-------------500-----0----------44,7%----20,2%-----
---2,5-------0,52----------500-----0----------10,5%----37,5%-----
(a)- MeOH
(b)- Benzene
(c)- EtOH
Catalytic hydrogenation freak