DR ANTHONY MELVIN CRASTO,WorldDrugTracker, helping millions, A 90 % paralysed man in action for you, I am suffering from transverse mylitis and bound to a wheel chair, With death on the horizon, nothing will not stop me except God................DR ANTHONY MELVIN CRASTO Ph.D ( ICT, Mumbai) , INDIA 25Yrs Exp. in the feld of Organic Chemistry,Working for GLENMARK GENERICS at Navi Mumbai, INDIA. Serving chemists around the world. Helping them with websites on Chemistry.Million hits on google, world acclamation from industry, academia, drug authorities for websites, blogs and educational contribution
Showing posts with label gamma-decalactone. Show all posts
Showing posts with label gamma-decalactone. Show all posts

Saturday 30 August 2014

Synthesis of gamma-decalactone from 1-octene and iodoacetic acid ethyl ester

1-Octene+Iodoacetic acid ethyl ester
Cu
reacts to


gamma-Decalactone
+

Iodoethane

Synthesis of gamma-decalactone from 1-octene and iodoacetic acid ethyl ester

(batch scale 10 mmol)

Substances
1-octen (bp 121 °C) 1.12 g (1.56 mL, 10.0 mmol)
iodoacetic acid ethyl ester (bp 73-74 °C/ 21 hPa) 2.78 g (1.54 mL, 13.0 mmol)
copper powder (finely powdered, > 230 mesh ASTM) 1.53 g (24.0 mmol)
tert-butyl methyl ether (bp 55 °C) 35 mL
Reaction
In a 50 mL two-neck flask with magnetic stir bar and a reflux condenser connected with a
protective gas piping 1.12 g (1.56 mL, 10.0 mmol) 1-octen are mixed with 2.78 g (1.54 mL,
13.0 mmol) iodoacetic acid ethyl ester and 1.53 g (24.0 mmol) copper powder under a
protective gas atmosphere. Afterwards the reaction mixture is stirred at 130 °C oil bath
temperature under protective gas for 2 hours under reflux. NOP http://www.oc-praktikum.de


Work up
The reaction mixture is cooled down to room temperature, diluted with 20 mL tert-butyl
methyl ether, stirred for 5 minutes and filtered off. The copper powder on the filter is washed
three times with 5 mL tert-butyl methyl ether each. Filtrate and wash solutions are combined,
the solvent is evaporated at the rotary evaporator. A liquid residue remains as crude product.
Crude yield: 1.5 g
The crude product is fractional distilled in a half-micro distillation apparatus under reduced
pressure.
Yield: 1.30 g ( 7.63 mmol, 77%); head temperature 85 °C (4.8·10-2 hPa, oil bath temperature
120 °C), colourless liquid; 20 nD = 1.4508




1H NMR

1H-NMR: gamma-Decalactone
500 MHz, CDCl3
delta [ppm]mult.atomsassignment
0.74t3 H10-H
1.12-1.20m8 H6-H, 7-H, 8-H, 9-H
1.39-1.77m3 H3-H, 5-Hb
2.18m1 H5-Ha
2.36dd2 H2-H
4.33tt1 H4-H
7.26CHCl3


13C NMR

13C-NMR: gamma-Decalactone
125.7 MHz, CDCl3
delta [ppm]assignment
13.9C10
22.4C9
25.0C5
27.9-29.0C6, C7, C8
31.5C3
35.4C2
80.9C4
177.1C1 (O-C(=O)-)
76.5-77.5CDCl3


IR

IR: gamma-Decalactone[Film, T%, cm-1][cm-1]assignment

Instruction (batch scale 100 mmol)
Equipment
100 mL two-neck flask, protective gas supply, reflux condenser, heatable magnetic stirrer,
magnetic stir bar, rotatory evaporator, high vacuum pump, distillation apparatus, oil bath
Substances
1-octen (bp 121 °C) 11.2 g (15.6 mL, 100 mmol)
iodoacetic acid ethyl ester (bp 73-74 °C/ 21 hPa) 27.8 g (15.4 mL, 130 mmol)
copper powder (finely powdered, > 230 mesh ASTM) 15.3 g (240 mmol)
tert-butyl methyl ether (bp 55 °C) 130 mL
 NOP http://www.oc-praktikum.de


Reaction
In a 100 mL two-neck flask with magnetic stir bar and a reflux condenser connected with a
protective gas piping 11.2 g (15.6 mL, 100 mmol) 1-octen are mixed with 27.8 g (15.4 mL,
130 mmol) iodoacetic acid ethyl ester and 15.1 g (240 mmol) copper powder under a protectiv
gas atmosphere. Afterwards the reaction mixture is stirred at 130 °C oil bath temperature
under protective gas for 6 hours under reflux.
Work up
The reaction mixture is cooled down to room temperature, diluted with 30 mL tert-butyl
methyl ether, stirred for 5 minutes and filtered off. The copper powder on the filter is washed
4 times with 25 mL tert-butyl methyl ether each. Filtrate and wash solutions are combined,
the solvent is evaporated at the rotary evaporator. A liquid residue remains as crude product.
Crude yield: 15.9 g
The crude product is fractional distilled under reduced pressure.
Yield: 13.5 g (79.3 mmol, 79%); head temperature 70 °C (1.7·10-2 hPa, oil bath temperature
120 °C), colourless liquid; 20 nD = 1.4508 

Operating scheme


Equipment

Batch scale:0.01 mol0.1 mol1-Octene
two-necked flask 50 mLtwo-necked flask 50 mLprotective gas pipingprotective gas piping
reflux condenserreflux condenserheatable magnetic stirrer with magnetic stir barheatable magnetic stirrer with magnetic stir bar
rotary evaporatorrotary evaporatorvacuum pumpvacuum pump
semi-micro distillation apparatussemi-micro distillation apparatusoil bathoil bath