Water → Phenyl cyanate

The title compound was prepared by a modification of the procedure described in Organic. Syntheses, 61, 35 (1983). A 3-necked, 2 L R.B. flask, equipped with a 500 ml pressure equalized dropping funnel, a mechanical stirrer and a thermometer, was charged with water and coled in an ice-salt bath. Cyanogen bromide (189.1 g, 1.78 mol) was added and the mixture was stirred for 5 min. Phenol (160.0 g., 1.7 mol) in carbon tetrachloride (535 ml) was added in one portion. The mixture was stirred vigorously while triethylamine (236.9 ml, 172.0 g, 1.7 mol) was added dropwise at a rate such that the reaction temperature did not exceed 5° C. (total addition time=45 min.). The mixture was stirred for a further 15 min. then transferred to a 2 L separatory funnell The organic layer was separated and the aqueous layer was extracted with carbon tetrachloride (2×90 ml). The combined organic layers were washed with water (3×90 ml) then dried by stirring with phosphorus pentoxide (10 g) for 15 min. The mixture was filtered and the solvent was evaporated under reduced pressure (water aspirator) at 20° C. to give a yellow oil. Polyphosphate ester (Y. Kanaoka, et al., Chem. Pharm. Bull., 13, 1065-1072 (1965)) (0.2 ml) was added and the mixture was distilled under reduced pressure through a 15 cm vigreux column to give phenyl cyanate (165.8 g, 82%) as a colorless oil, b.p. 79°-82° C. (16 mmHg)1. The product was stored under nitrogen at -10° C. (freezes).

1. customThe title compound was prepared by a modification of the procedure
2. customflask, equipped with a 500 ml pressure
3. customcoled in an ice-salt bath
4. additionwas added dropwise at a rate such that the reaction temperature
5. customdid not exceed 5° C.
6. addition(total addition time=45 min.)
7. stirringThe mixture was stirred for a further 15 min.
8. customwas separated
9. extractionthe aqueous layer was extracted with carbon tetrachloride (2×90 ml)
10. washThe combined organic layers were washed with water (3×90 ml)
11. customthen dried
12. stirringby stirring with phosphorus pentoxide (10 g) for 15 min
13. filtrationThe mixture was filtered
14. customthe solvent was evaporated under reduced pressure (water aspirator) at 20° C.
15. customto give a yellow oil
16. distillationthe mixture was distilled under reduced pressure through a 15 cm vigreux column

ORD record

ord-0e4735efef654a35bcd736238a290eb5

Source dataset

uspto-grants-1997_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US05633247