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Sunday, 31 August 2014

Synthesis of 9,10-dihydro-9,10-ethanoanthracene-11,12-trans-dicarboxylic acid diethyl ester

Anthracene+Fumaric acid diethyl ester
reacts to
9,10-Dihydro-9,10-ethanoanthracene-11,12-trans-dicarboxylic acid diethyl ester

Synthesis of 9,10-dihydro-9,10-ethanoanthracene-11,12-trans-dicarboxylic acid diethyl ester

Reaction type:cycloaddition, Diels-Alder reaction
Substance classes:alkene, aromatics, carboxylic acid ester, diene, dienophile, acid catalyst
Techniques:working with moisture exclusion, heating under reflux, stirring with magnetic stir bar, filtering, evaporating with rotary evaporator, recrystallizing, use of an ice cooling bath, heating with oil bath



Operating scheme

Operating scheme


Equipment

Batch scale:0.01 mol0.1 molAnthracene
three-necked flask 100 mLthree-necked flask 100 mLadapter with ground-glass joint and hose couplingadapter with ground-glass joint and hose coupling
protective gas pipingprotective gas pipingreflux condenserreflux condenser
drying tubedrying tubebubble counterbubble counter
powder funnelpowder funnelheatable magnetic stirrer with magnetic stir barheatable magnetic stirrer with magnetic stir bar
rotary evaporatorrotary evaporatorice bathice bath
exsiccator with drying agentexsiccator with drying agentoil bathoil bath


1H NMR

1H-NMR: 9,10-Dihydro-9,10-ethanoanthracene-11,12-trans-dicarboxylic acid diethyl ester
250 MHz, CDCl3
delta [ppm]mult.atomsassignment
1.23t (3J = 7.2 Hz)6 HCH3 ethyl
3.45m2 H11-H, 12-H (-CH-COO-)
4.08m4 HCH2 ethyl
4.75m2 H9-H, 10-H
7.09-7.38m8 HCH (arom.)
>7.4CH (arom., educt)

13C NMR


13C-NMR: 9,10-Dihydro-9,10-ethanoanthracene-11,12-trans-dicarboxylic acid diethyl ester
62.5 MHz, CDCl3
delta [ppm]assignment
14.2CH3 (ethyl ester)
46.7C9, C10 (CH)
47.7C11, C12 (CH-COO)
60.9CH2 (ethyl ester)
123.8CH arom.
124.5CH arom.
126.2CH arom.
126.3CH arom.
140.3C quart. arom.
142.0C quart. arom.
172.3C(=O)O-
76.5-77.5CDCl3

IR


IR: 9,10-Dihydro-9,10-ethanoanthracene-11,12-trans-dicarboxylic acid diethyl ester
[KBr, T%, cm-1]
[cm-1]assignment
3074, 3026arom. C-H valence
2981aliph. C-H valence
2935, 2897aliph. C-H valence
1739C=O valence, ester
1467arom. C=C valence


Instruction (batch scale 100 mmol) 
Equipment 
1000 mL three-neck flask, adapter with ground glass joint and hose coupling, protective gas 
supply, reflux condenser, drying tube, bubble counter, powder funnel, heatable magnetic 
stirrer, magnetic stir bar, rotary evaporator , ice bath, desiccator, oil bath 
Substances 
anthracene (mp 215-217 °C9 17.8 g (100 mmol) 
fumaric acid diethyl ester (bp 219 °C) 17.2 g (16.4 mL, 100 mmol) 
aluminium chloride (water free) 13.3 g (100 mmol) 
cyclohexane (water free) (bp 81 °C) 500 mL 
cyclohexane (bp 81 °C) 200 mL 
sodium carbonate decahydrate 24.9 g (150 mmol) 
sodium carbonate (water free) 25.0 g (236 mmol) 
ethanol (bp 78 °C) 150 mL 

Reaction 
The reaction apparatus consists of a thoroughly dried 1000 mL three-neck flask with reflux 
condenser, drying tube and magnetic stir bar. On one opening of the flask is placed an adapter 
with ground glass joint and hose coupling as inlet for nitrogen. This adapter is replaced 
through a glass stopper after the addition of aluminium chloride to the flask. The reaction 
apparatus is flushed with nitrogen. Then under stirring 17.8 g (100 mmol) anthracene and 
17.2 g (16.4 mL, 100 mmol) fumaric acid diethyl ester are dissolved in the flask in 500 mL 
absolute cyclohexane. After cooling down in the ice bath 13.3 g (100 mmol) water-free 
aluminium chloride are added in one portion over a powder funnel under nitrogen counter 
flow. The reaction mixture is heated under stirring for four hours under reflux. 
Work up 
The reaction mixture is cooled down to room temperature, then 24.9 g (150 mmol) sodium 
carbonate decahydrate are added. The drying tube is replaced through a bubble counter filled 
with paraffin oil and the mixture is stirred until no more gas is formed. Then 25 g (236 mmol) 
sodium carbonate (water free) are added. The mixture is stirred for 10 minutes. The solid is 
filtered off and washed in portions with a total of 200 mL cyclohexane. The solvent is 
evaporated from the filtrate at a rotary evaporator. A solid residue remains as crude product, 
which is dried in the desiccator. Crude yield: 32.6 g 
The crude product is recrystallized from about 150 mL ethanol. 
Yield: 30.8 g (87.9 mmol, 88%); colourless crystals, mp 103 °C




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