Green Chemistry Approaches to Condensation Reactions of Formylferrocene
1. Green Chemistry Approaches to Condensation Reactions of Formylferrocene with Active
Methylene-Containing Compounds
Research of Yinjuan Bai*, Jun Lu*, Haiying Gan*, Zhenjun Wang*, and Zhen Shi*, presented by Alexandra Uihlein
*Department of Chemistry, Northwest University, Xi’an, P.R. China
0.43 g of formylferrocene (1) and a methylene
compound (2) (2 mmol for the synthesis of 3 or 1 mmol
for the synthesis of 4) were mixed in 20 mL of water. The
water was stirred at 95-100°C (60-65°C for the synthesis
of 3g and 3h) for 45 minutes. The solid was filtered and
washed with boiling water. The impure products 3a-3e
were collected via vacuum filtration. The solid products
3f-3h, 4g and 4h were synthesized in a base with pH of
12-13. After, the mixture was extracted with CHCl3 and
washed with distilled water.¹
With increasing environmental attention in recent years, green chemistry has been a growing field. In many organic reactions, toxic byproducts are created that are dangerous to
humans and the environment. New ways to create organic compounds without also creating toxic byproducts are necessary to environmental conservation. Ferrocene and its
derivatives, including formylferrocene, are useful for creating organometallic nonlinear optical polymers and for combusting composite explosives. In this investigation,
formylferrocene is reacted with methylene compounds to create ferrocenylmethylene-containing compounds.
0.43 g of formylferrocene (1), a methylene
compound (2) (2 mmol of 2a-2f or 1 mml of 2g-
2h), and 0.11 g of potassium hydroxide were
ground together until the reactants were fully
reacted together. The solid product was washed
with hot water and dried though vacuum
filtration.¹
0.43 g of formylferrocene (1), a methylene compound
(2) (2 mmol of 2a-2d or 3 mmol of 2e-2f or 1.5 mmol
of 2g-2h), and 0.11 g of potassium hydroxide (2a-2d
did not need KOH) were mixed in a beaker covered
with a watch glass. The covered beaker was put in a
household microwave oven and heated for a specific
time at a specific power level (See Table 1).¹
After each procedure, the products 3a-3e of each procedure were separated using recrystallization in an
ethanol/water mixture with a 3:1 ratio, respectively. The products 3f-3h, 4g and 4h were submitted
through silica-gel column chromatography, comprised of petroleum ether/ethoxy acetate with a 10:1
ratio.¹
3a: 5-ferrocenylmethylenebarbituric acid 3f: 3-ferrocenylmethylene-2,4-pentandione
3b: 5-ferrocenylmethylenethiobarbituric acid 3g: 2-ferrocenylmethylenecyclohexanone
3c: 2,2-dimethyl-5-ferrocenylmethylene-1,3-dioxane-4,6-dione 3h: 2-ferrocenylmethylenecyclopentanone
3d: 1-phenyl-3-methyl-4-ferrocenylmethylenepyrazole-5-one 4g: 2,5-diferrocenylmethylenecyclohexanone
3e: ethyl 1-ferrocenylmethylenecyanoacetate 4h: 2,4-diferrocenylmethylenecyclopentanone
Regerences
Yinjuan, B.; Lu, J.; Gan, H.; Wang, Z.; Shi, Z. Green Chemistry Approaches to Condensation Reactions of Formylferrocene with Active Methylene Compounds. Syn. React.
Inorg. Met. [Online] 2004. 34, 1487-1496.
http://www.researchgate.net/publication/216248185_Green_Chemistry_Approaches_to_Condensation_Reactions_of_Formylferrocene_with_Active_Methylene_Contain
ing_Compounds (accessed Nov 19, 2013).
Figure 2: A list and models of all the reactants and products.¹
Figure 1: Diagram of a vacuum filter. The solid product was
placed in the crucible and, when the vacuum was turned on,
the water was removed from the solid, leaving it dry.
(http://s169.photobucket.com/user/Kazk1287/media/VacuumFiltration.gif.html)
3a-3e had the highest yields in all three of the procedures. Each
procedure yielded approximately the same percentage of each of
the products 3a-3e. Products 3g and 3h were not produced
though dry grinding or microwave irradiation, but in water, each
product was produced at about 50% yield. Products 4g and 4h
were produced in all three procedures, but the synthesis in
water produced the highest percent yield of both products.
Table 1: Results of each procedure.¹
Discussion
Products
Procedure for Synthesis in Water Procedure for Dry Grinding Synthesis Procedure for Dry Synthesis for
Microwave Irradiation
Introduction
![Green Chemistry Approaches to Condensation Reactions of Formylferrocene with Active
Methylene-Containing Compounds
Research of Yinjuan Bai*, Jun Lu*, Haiying Gan*, Zhenjun Wang*, and Zhen Shi*, presented by Alexandra Uihlein
*Department of Chemistry, Northwest University, Xi’an, P.R. China
0.43 g of formylferrocene (1) and a methylene
compound (2) (2 mmol for the synthesis of 3 or 1 mmol
for the synthesis of 4) were mixed in 20 mL of water. The
water was stirred at 95-100°C (60-65°C for the synthesis
of 3g and 3h) for 45 minutes. The solid was filtered and
washed with boiling water. The impure products 3a-3e
were collected via vacuum filtration. The solid products
3f-3h, 4g and 4h were synthesized in a base with pH of
12-13. After, the mixture was extracted with CHCl3 and
washed with distilled water.¹
With increasing environmental attention in recent years, green chemistry has been a growing field. In many organic reactions, toxic byproducts are created that are dangerous to
humans and the environment. New ways to create organic compounds without also creating toxic byproducts are necessary to environmental conservation. Ferrocene and its
derivatives, including formylferrocene, are useful for creating organometallic nonlinear optical polymers and for combusting composite explosives. In this investigation,
formylferrocene is reacted with methylene compounds to create ferrocenylmethylene-containing compounds.
0.43 g of formylferrocene (1), a methylene
compound (2) (2 mmol of 2a-2f or 1 mml of 2g-
2h), and 0.11 g of potassium hydroxide were
ground together until the reactants were fully
reacted together. The solid product was washed
with hot water and dried though vacuum
filtration.¹
0.43 g of formylferrocene (1), a methylene compound
(2) (2 mmol of 2a-2d or 3 mmol of 2e-2f or 1.5 mmol
of 2g-2h), and 0.11 g of potassium hydroxide (2a-2d
did not need KOH) were mixed in a beaker covered
with a watch glass. The covered beaker was put in a
household microwave oven and heated for a specific
time at a specific power level (See Table 1).¹
After each procedure, the products 3a-3e of each procedure were separated using recrystallization in an
ethanol/water mixture with a 3:1 ratio, respectively. The products 3f-3h, 4g and 4h were submitted
through silica-gel column chromatography, comprised of petroleum ether/ethoxy acetate with a 10:1
ratio.¹
3a: 5-ferrocenylmethylenebarbituric acid 3f: 3-ferrocenylmethylene-2,4-pentandione
3b: 5-ferrocenylmethylenethiobarbituric acid 3g: 2-ferrocenylmethylenecyclohexanone
3c: 2,2-dimethyl-5-ferrocenylmethylene-1,3-dioxane-4,6-dione 3h: 2-ferrocenylmethylenecyclopentanone
3d: 1-phenyl-3-methyl-4-ferrocenylmethylenepyrazole-5-one 4g: 2,5-diferrocenylmethylenecyclohexanone
3e: ethyl 1-ferrocenylmethylenecyanoacetate 4h: 2,4-diferrocenylmethylenecyclopentanone
Regerences
Yinjuan, B.; Lu, J.; Gan, H.; Wang, Z.; Shi, Z. Green Chemistry Approaches to Condensation Reactions of Formylferrocene with Active Methylene Compounds. Syn. React.
Inorg. Met. [Online] 2004. 34, 1487-1496.
http://www.researchgate.net/publication/216248185_Green_Chemistry_Approaches_to_Condensation_Reactions_of_Formylferrocene_with_Active_Methylene_Contain
ing_Compounds (accessed Nov 19, 2013).
Figure 2: A list and models of all the reactants and products.¹
Figure 1: Diagram of a vacuum filter. The solid product was
placed in the crucible and, when the vacuum was turned on,
the water was removed from the solid, leaving it dry.
(http://s169.photobucket.com/user/Kazk1287/media/VacuumFiltration.gif.html)
3a-3e had the highest yields in all three of the procedures. Each
procedure yielded approximately the same percentage of each of
the products 3a-3e. Products 3g and 3h were not produced
though dry grinding or microwave irradiation, but in water, each
product was produced at about 50% yield. Products 4g and 4h
were produced in all three procedures, but the synthesis in
water produced the highest percent yield of both products.
Table 1: Results of each procedure.¹
Discussion
Products
Procedure for Synthesis in Water Procedure for Dry Grinding Synthesis Procedure for Dry Synthesis for
Microwave Irradiation
Introduction](https://image.slidesharecdn.com/1db82378-8f99-42c5-9889-2eaa710a6890-160112211538/85/Green-Chemistry-Approaches-to-Condensation-Reactions-of-Formylferrocene-1-320.jpg)
