skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Fluorination of organic compounds with K{sub 2}NiF{sub 6} and R-NiF{sub 3}. Synthesis and characterization of the novel fluorinated cation: (CHF{sub 2}){sub 4}N{sup +}

Abstract

The Simons Process electrochemical fluorination of organic compounds is speculated to involve a higher nickel fluoride, NiF{sub x} (X>2), which is formed at the nickel anode. To investigate this possibility, K{sub 2}NiF{sub 6} and R-NiF{sub 3} have been used in aHF solution to fluorinated CH{sub 3}CN, CH{sub 3}COF, (CH{sub 3}){sub 2}CO, CH{sub 3}C(O)NH{sub 3}{sup +}PF{sub 6}{sup -}, N{sub 2}O, NH{sub 4}{sup +}AsF{sub 6}, and (CH{sub 3}){sub 4}N{sup +} AsF{sub 6}{sup -}. Organic compounds were reacted with solutions (K{sub 2}NiF{sub 6}) or suspensions (R-NiF{sub 3}) of oxidizer below -60 {degrees}C ({approximately}3 h) then slowly warmed to room temperature. The products were characterized by {sup 1}H, {sup 19}F, {sup 13}C, and {sup 14}N NMR. CH{sub 3}CN yielded primarily CF{sub 3}CN with R-NiF{sub 3} and CF{sub 3}CF{sub 2}NF{sub 2} with K{sub 2}NiF{sub 6}, along with small amounts of fluorocarbons. CH{sub 3}COF and (CH{sub 3}){sub 2}CO underwent cleavage, yielding small amounts of CF{sub 3}COF and (CF{sub 3}){sub 2}CO but with COF{sub 2} and fluorocarbons as the major products. CH{sub 3}C(O)NH{sub 3}{sup +} also underwent cleavage reactions. N{sub 2}O and NH{sub 4}{sup +} were unreactive with either oxidizer. (CH{sub 3}){sub 4}N{sup +} yielded the novel fluorinated cation, (CHF{sub 2}){sub 4}N{sup +} with K{sub 2}NiF{sub 6}.

Authors:
; ;  [1]
  1. Lawrence Berkeley National Lab., CA (United States)
Publication Date:
OSTI Identifier:
560030
Report Number(s):
CONF-970443-
TRN: 97:005895-0107
Resource Type:
Conference
Resource Relation:
Conference: 213. national meeting of the American Chemical Society, San Francisco, CA (United States), 13-17 Apr 1997; Other Information: PBD: 1997; Related Information: Is Part Of 213th ACS national meeting; PB: 2904 p.
Country of Publication:
United States
Language:
English
Subject:
40 CHEMISTRY; FLUORINATION; ORGANIC COMPOUNDS; SUSPENSIONS; SYNTHESIS; NICKEL FLUORIDES; POTASSIUM FLUORIDES; NMR SPECTRA

Citation Formats

Chacon, L C, Whalen, J M, Bartlett, N, and Univ. of California, Berkeley, CA. Fluorination of organic compounds with K{sub 2}NiF{sub 6} and R-NiF{sub 3}. Synthesis and characterization of the novel fluorinated cation: (CHF{sub 2}){sub 4}N{sup +}. United States: N. p., 1997. Web.
Chacon, L C, Whalen, J M, Bartlett, N, & Univ. of California, Berkeley, CA. Fluorination of organic compounds with K{sub 2}NiF{sub 6} and R-NiF{sub 3}. Synthesis and characterization of the novel fluorinated cation: (CHF{sub 2}){sub 4}N{sup +}. United States.
Chacon, L C, Whalen, J M, Bartlett, N, and Univ. of California, Berkeley, CA. Wed . "Fluorination of organic compounds with K{sub 2}NiF{sub 6} and R-NiF{sub 3}. Synthesis and characterization of the novel fluorinated cation: (CHF{sub 2}){sub 4}N{sup +}". United States.
@article{osti_560030,
title = {Fluorination of organic compounds with K{sub 2}NiF{sub 6} and R-NiF{sub 3}. Synthesis and characterization of the novel fluorinated cation: (CHF{sub 2}){sub 4}N{sup +}},
author = {Chacon, L C and Whalen, J M and Bartlett, N and Univ. of California, Berkeley, CA},
abstractNote = {The Simons Process electrochemical fluorination of organic compounds is speculated to involve a higher nickel fluoride, NiF{sub x} (X>2), which is formed at the nickel anode. To investigate this possibility, K{sub 2}NiF{sub 6} and R-NiF{sub 3} have been used in aHF solution to fluorinated CH{sub 3}CN, CH{sub 3}COF, (CH{sub 3}){sub 2}CO, CH{sub 3}C(O)NH{sub 3}{sup +}PF{sub 6}{sup -}, N{sub 2}O, NH{sub 4}{sup +}AsF{sub 6}, and (CH{sub 3}){sub 4}N{sup +} AsF{sub 6}{sup -}. Organic compounds were reacted with solutions (K{sub 2}NiF{sub 6}) or suspensions (R-NiF{sub 3}) of oxidizer below -60 {degrees}C ({approximately}3 h) then slowly warmed to room temperature. The products were characterized by {sup 1}H, {sup 19}F, {sup 13}C, and {sup 14}N NMR. CH{sub 3}CN yielded primarily CF{sub 3}CN with R-NiF{sub 3} and CF{sub 3}CF{sub 2}NF{sub 2} with K{sub 2}NiF{sub 6}, along with small amounts of fluorocarbons. CH{sub 3}COF and (CH{sub 3}){sub 2}CO underwent cleavage, yielding small amounts of CF{sub 3}COF and (CF{sub 3}){sub 2}CO but with COF{sub 2} and fluorocarbons as the major products. CH{sub 3}C(O)NH{sub 3}{sup +} also underwent cleavage reactions. N{sub 2}O and NH{sub 4}{sup +} were unreactive with either oxidizer. (CH{sub 3}){sub 4}N{sup +} yielded the novel fluorinated cation, (CHF{sub 2}){sub 4}N{sup +} with K{sub 2}NiF{sub 6}.},
doi = {},
journal = {},
number = ,
volume = ,
place = {United States},
year = {1997},
month = {12}
}

Conference:
Other availability
Please see Document Availability for additional information on obtaining the full-text document. Library patrons may search WorldCat to identify libraries that hold this conference proceeding.

Save / Share: