2-(3-Nitrophenyl)-1,3-dioxolane [6952-67-6]
1H-NMR
| 1H-NMR: 2-(3-Nitrophenyl)-1,3-dioxolane | |||
| 250 MHz, CDCl3 | |||
| interactive spectrum | |||
| delta [ppm] | mult. | atoms | assignment |
| 4.05-4.18 | m | 4 H | -OCH2CH2O- |
| 5.90 | s | 1 H | O-CH-O |
| 7.54-7.60 | m | 1 H | 5-H |
| 7.79-7.83 | m | 1 H | 6-H |
| 8.20-8.25 | m | 1 H | 4-H |
| 8.35-8.37 | m | 1 H | 2-H |
| 7.26 | CHCl3 | ||
| 10.15 | s | 1 H | CHO (educt) |
13C-NMR |
| 13C-NMR: 2-(3-Nitrophenyl)-1,3-dioxolane | |||
| 250 MHz, CDCl3 | |||
| interactive spectrum | |||
| delta [ppm] | assignment | ||
| 65.5 | -OCH2CH2O- | ||
| 102.3 | -O-CH-O- | ||
| 121.7 | C2 | ||
| 124.0 | C4 | ||
| 129.4 | C5 | ||
| 132.7 | C6 | ||
| 140.4 | C1 | ||
| 148.3 | C3 | ||
| 76.5-77.5 | CDCl3 | ||
IR
| IR: 2-(3-Nitrophenyl)-1,3-dioxolane | |||
| [KBr, T%, cm-1] | |||
| [cm-1] | assignment | ||
| 3093 | arom. C-H valence | ||
| 2978 | aliph. C-H valence | ||
| 2905, 2862 | C-H valence | ||
| 2769 | C-H valence, O-CH-O | ||
| 1621, 1588 | arom. C=C valence | ||
| 1532, 1359 | N=O valence | ||
| 1532, 1359 | N=O valence | ||
Acid catalyzed acetalisation of 3-nitrobenzaldehyde with ethanediol to the correspondent 1,3-dioxolane
 | + |  |
|  | + |  | ; Side reactions |
Acid catalyzed acetalisation of 3-nitrobenzaldehyde with ethanediol to the correspondent 1,3-dioxolane
|
| Reaction type: | reaction of the carbonyl group in aldehydes, acetalisation |
| Substance classes: | aldehyde, acetal, alcohol, protecting group, acid catalyst |
| Techniques: | removal of water by azeotropic distillation, heating under reflux with Soxhlet extractor (for 10 mmol preparation), stirring with magnetic stir bar, evaporating with rotary evaporator, shaking out, extracting, recrystallizing, filtering, heating with oil bath |
Reaction
3-Nitrobenzaldehyde (15.1 g, 100 mmol), ethanediole (6.83 g, 6.20 mL, 110 mmol) and 4-toluenesulfonic acid monohydrate (1.00 g, 5.30 mmol)
 are dissolved in cyclohexane (200 mL) in a dry 500 mL round bottom flask equipped with magnetic stirring bar, Dean Stark trap and reflux condenser. The reaction mixture is refluxed until no more water  is collected in the Dean-Stark trap (approx. 2-3 h ).Work up
The hot reaction mixture is poured into another 500 mL round bottom flask to separate it from an oily sediment (800 mg) which has formed at the bottom of the reaction vessel. The sediment consists predominantly of product, starting material and 4-toluenesulfonic acid (1H-NMR spectrum). The solvent of the decanted solution is directly removed with a rotary evaporator
. A yellow crystalline solid remains as crude product.
Crude product yield: 19.7 g; melting point 50-52 °C; Purity according to GC: 95% acetale + 4% aldehyde
In order to remove unreacted aldehyde as hydrogensulfite adduct, the crude product is dissolved in 200 mL tert-butyl methyl ether and extracted once with 20 mL saturated aqueous sodium hydrogen sulfite solution. The organic phase is dried over sodium sulfate, the sodium sulfate is removed by filtration and the solvent is evaporated with a rotary evaporator
to yield a nearly colorless crystalline residue.
Yield: 17.9 g; melting point 57-58 °C; Purity according to GC: more than 99%.
The product is for most uses pure enough. If further purification is required, recrystallization from a solvent mixture of cyclohexane / tert-butyl methyl ether in a ratio of 1:1 (approximately 45 mL) can be carried out. The solution should be allowed to stand covered at room temperature until crystals form (if needed 1 to 2 days). If the solution is cooled quickly in an ice bath, only an oil generally forms. After cooling for a short time in an ice bath, the crystals are filtered and dried until constant mass is achieved in a desiccator at reduced pressure.
Yield: 15.9 g; melting point 57-58 °C; colorless crystals; purity according to GC: more than 99%.
The product can also be recrystallized from a small amount of hot ethanol, however with a much poorer yield.
Duration of the experiment
Approximately 5 hours including work up.
Where can I stop the experiment?
After evaporation of the cyclohexane from the reaction solution.
Recycling
The cyclohexane from the reaction mixture and the tert-butyl methylether are collected and redistilled.
|
Suggestions for waste disposal | ||||||||||||
|
Substances required |
| Educts | Amount | Risk | Safety | ||||||
|---|---|---|---|---|---|---|---|---|---|
| 3-Nitrobenzaldehyde |
| 15.1 g | H302 H411 | P273 | |||||
| 1,2-Ethanediol |
| 6.83 g | H302 | P301 + 312 | |||||
| Catalyst | Amount | Risk | Safety | ||||||
| 4-Toluenesulfonic acid monohydrate |
| 0.19 g | H315 H319 H335 | P261 P305 + 351 + 338 | |||||
| Solvents | Amount | Risk | Safety | ||||||
| Cyclohexane |
| ~ 230 mL | H225 H304 H315 H336 H410 | P210 P233 P240 P273 P301 + 310 P302 + 352 P331 P403 + 235 | |||||
| tert-Butyl methyl ether |
| 230 mL | H225 H315 | P210 | |||||
| Others | Amount | Risk | Safety | ||||||
| Sodium disulfite |
| ~ 13 g | H302 H318 EUH031 | P280 P305 + 351 + 338 P313 | |||||
| Sodium sulfate |
| ~ 5 g | |||||||
| Molecular sieve 4A |
| 0 g | H315 H319 H335 | P261 P305 + 351 + 338 | |||||
| Solvents for analysis | Amount | Risk | Safety | ||||||
| tert-Butyl methyl ether |
| 5 mL | H225 H315 | P210 |
Substances produced |
| Products | Amount | Risk | Safety | ||
|---|---|---|---|---|---|
| 2-(3-Nitrophenyl)-1,3-dioxolane | 17.9 g | ||||
| Water | H- EUH- | P- |
Equipment |
 | round bottom flask 100 mL |  | Soxhlet extractor 30 mL | |
 | extraction cone |  | reflux condenser | |
 | heatable magnetic stirrer with magnetic stir bar |  | separating funnel | |
 | rotary evaporator |  | suction flask | |
 | Hirsch funnel |  | exsiccator with drying agent | |
 | oil bath |
| Waste | Disposal |
|---|---|
| aqueous phase from water separator | solvent water mixtures, halogen free |
| aqueous phase from shaking out | solvent water mixtures, halogen free |
| dissolve residue from reaction flask in a small amount of acetone | organic solvents, halogen free |
| mother liquor from recrystallisation | organic solvents, halogen free |
| sodium sulfate | solid waste, free from mercury |
Simple evaluation indices |
| Atom economy | 91.5 | % | |
| Yield | 93 | % | |
| Target product mass | 1.82 | g | |
| Sum of input masses | 74 | g | |
| Mass efficiency | 24 | mg/g | |
| Mass index | 41 | g input / g product | |
| E factor | 40 | g waste / g product | |
| Energy input | 870 | kJ | |
| Energy efficiency |
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The classical variant of the "Acid catalyzed acetalisation of 3-nitrobenzaldehyde with ethanediol to the correspondent 1,3-dioxolane" is an easily performed experiment. The desired product is obtained in high yield  and high selectivity. Also the purity of the end product is very high.The mass efficiency is high to medium, compared to the other NOP experiments and thus evaluates as good . The energy efficiency of the classical experiment is highly dependent on the method of heating .
(Eco)toxicological data for the educt 3-nitrobenzaldehyde are incomplete, toxicological data for the product 2-(3-nitrophenyl)-1,3-dioxolane have not been determined at all. According to theoretical prediction methods both product and educt are suspected to have mutagenic, carcinogenic and sensitizing properties. The organic solvents used in this experiment ethanol,cyclohexane and tert-butyl methyl ether exhibit relatively low acute toxicity. Also the inorganic auxiliary materials do not pose significant dangers to human health
.
Educt, product and the solvents cyclohexane and tert-butyl methyl ether are biologically not easily degradable, and some are classified as dangerous to the environment because of their toxicity to aquatic organisms
.
Summed up we evaluate this experiment with a good economic efficiency and acceptable toxicological risks, but a relatively high environmental persistence of the used substances with the "yellow light".
|
Chromatogram |
| GC: crude product | |
| column | Zebron ZB-1, L=15 m, d=0.25 mm, film 0.25 µm (Phenomenex) |
| inlet | injector: 250°C, split injection, 0.15 µL |
| carrier gas | He, pre-column pressure 101 kPa |
| oven | 85°C (0 min), 8°C/min --> 250°C (10 min) |
| detector | FID, 250°C, H2 33.9 mL/min, synth. air 322 mL/min, isocratic N2, 15 mL/min (59 kPa) |
| integration | percent concentration calculated from relative peak area |
| GC: pure product | |
| column | Zebron ZB-1, L=15 m, d=0.25 mm, film 0.25 µm (Phenomenex) |
| inlet | injector: 250°C, split injection, 0.15 µL |
| carrier gas | He, pre-column pressure 101 kPa |
| oven | 85°C (0 min), 8°C/min --> 250° C (10 min) |
| detector | FID 250°C, H2 33.9 mL/min, synth. air 322 mL/min, isocratic N2, flow 15 mL/min (59 kPa) |
| integration | percent concentration calculated from relative peak area |
.
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