Dimethylformamide → HCID 14816499, compound

Temperature

0 °C

The iodomethyl 2-(trimethylsilyloxy)ethyl ether solution prepared in example 2 was kept in a dry ice-acetone bath and a dry solution of nitroform (76 g; 0.5 moles) in 375 ml of methylene chloride was added over 20 minutes through an addition funnel. [See Example 5 for the preparation of the nitroform solution]. After the addition of the nitroform-methylene chloride solution was complete, dry dimethylformamide (100 ml) was added and after five minutes the reaction solution was removed from the dry ice-acetone bath and allowed to warm to near 0° C. (takes about 45 minutes). The solution was then cooled in an ice bath for 15 minutes before it was poured into 600 ml of ice water. The lower organic layer was separated after which the aqueous phase was extracted with 3×25 ml of methylene chloride. The combined organic extracts were dried over sodium sulfate and then allowed to stand in a hood in a current of air to remove volatiles. The residue (approximately 150 g but depends on the amount of dimethylformamide lost) contains mainly 2,2,2-trinitroethyl 2-hydroxyethyl ether1 and dimethylformamide along with much smaller amounts of two byproducts2 (A and B). The crude ether was added to 46 ml of concentrated hydrochloric acid and the mixture was stirred well at 60°-65° C. for 1 hour. After cooling to room temperature, 30 ml of methylene chloride was added and the organic layer was separated and washed with 3×30 ml of water. The combined water extracts (90 ml) were back extracted with methylene chloride (30 ml) and the combined organic extracts were dried over sodium sulfate.

1. customwas removed from the dry ice-acetone bath
2. temperatureThe solution was then cooled in an ice bath for 15 minutes before it
3. additionwas poured into 600 ml of ice water
4. customThe lower organic layer was separated after which the aqueous phase
5. extractionwas extracted with 3×25 ml of methylene chloride
6. dry with materialThe combined organic extracts were dried over sodium sulfate
7. customto remove volatiles
8. additionThe crude ether was added to 46 ml of concentrated hydrochloric acid
9. temperatureAfter cooling to room temperature
10. addition30 ml of methylene chloride was added
11. customthe organic layer was separated
12. washwashed with 3×30 ml of water
13. extractionwere back extracted with methylene chloride (30 ml)
14. dry with materialthe combined organic extracts were dried over sodium sulfate

ORD record

ord-a66b13784f0c45c78e7070b93c93e0ec

Source dataset

uspto-grants-1989_06

DOI

10.6084/m9.figshare.5104873.v1

Patent number

USH0000644