secondary cells with lithium anodes and immobilized fused_salt
secondary cells with lithium anodes and immobilized fused_salt secondary cells with lithium anodes and immobilized fused_salt
Introduction 56. FLUORODINITROETUNOL AND DERIVATIVGS" Henry J. Marcus Aerojet-Ceneral Corporation, Azusa, California The chemistry of 2-fluor0-2,2-dinitroethanol has been investigated for tho past several years, and it is a privilege to present some of this material at thia time. This paper presents a 31.1nmary of a process evaluation study, and much of the chemistry involved will be reported in greater detail by the original authors in the coming months. It may be stated at the outset that the chemistry of fluorodinitromethyl ,compounds shows marked similarity to trinitromethyl or e-dinitromethyl compounds, which are well-known in the literatureo Synthesis of 2-Fluoro-2.2-dinitroethanol . One preparative method for 2-fluoro-2,2-dinitroethanol (FDNE) is based on tho fluorination of the aci-sodium salt of dinitroethanol NO,@Na@ n L :02 F2(or C103F) + C - CH20H FC CH20H I N02 The starting material fcr Reaction (1) is prepared in situ by the deformylation of 2,2-dinitro-l,Fpropanediol with one mole of base NO2 y 2 N02%a@ n + NaOH C CH20H 11 Compound I1 is preferably prepared by the oxidative nitration of Z-nitro-l,Fpropanediol (Reference 1). I1 is not isolated, but is partially purified by extraction from the aqueous reaction mixture with ethyl or isopropyl ether, followed by an extraction of the ether solution with aqueoue base, which converts I1 to the aci-sodium ealt of dinitroethanol. Although other methods of preparation of I1 are known, tho route shown was the one of choice. Conversion of I1 to FDNE was carried out by introducing fluorine gas, diluted 1:l with nitrogen, into the ahueoue solution of the aci-sodium salt at 15 to 25O (Reference 2). It was found that efficient dispersion of the fluorine is eseential, and that stainlesa steel gas-inlet tubes with open ends of 1/4 or 3/8 in., or with various hole aizee of 0.016 to 0.040, are eatisfactory in a 50-liter vessel. Th amaller the diameter of the holes, however, the more frequently were they occluded by soaim fluoride. I N02 A rapid injection of water served to remove the obstruction. This report ie based on work supported, in large part, by the AEC through the Lawrence Radiation Laboratory of the University of California.
Yields of 60 to 7046 of FDNE were generally obtained, although about l& Of the 57. theoretical quantity of fluorine was consumed. The pH of the solution was not a critical factor, so long as it was maintained at or ab&e the 7.5 to 8.0 level. The same results were obtained whether the pH was maintained at 8.0 or whether fluorination was begun at a pH of about 11, and the solution allowed to go acid; in the latter case, however, it was sometimes necessary to add alkali and to continue the fluorination Ethyl ether was found to be very efficient in extracting FDNE froa the aqueous fluorination mixture. However, it tends to extract some impurities along with tho FDNE. For example, one of the contaminants found in the fluorination of 11 was identified as 2,2,4,4-tetranitro-1,5-pentanediol (Reference 3). It was obtained in rather significant quantity (3 to 5 percent) from an ether extract of FINE, from a batch in which most of the FDNE had previously been extracted with methylene ,chloride. 'In actual practice, sodium chloride is added to decrease the solubility of FDNE in the aqueous medium, and methylene chloride, with a far less favorable distribution coefficient than ether, is used as the extractant. The crude product ob tained by removing the solvent is generally 80 to 90 mole-percent pure, as analyzed by gas chromatography. An alternate method for preparing FDNE consists of the fluorination of nitroform, followed by reduction with alkaline peroxide and the Henry reaction with formaldehyde (References 2 and 4). FC(N02)3 + H202 + HCHO - I11 FDNE OIP The fluorination of nitroform is carried out under conditions similar to those described for the aci-sodium salt of dinitroethanol, but the yields are superior (80 to 9Q% of theory), and the isolation of the product presents little difficulty; I11 is essentially insoluble in water. and, following mild washing, is obtained in 98 mole-percent purity (gas chromatography). A slight source of difficulty is presented by the emulsified interface, but this problem can be overcome by vacuum fil- tration and water-washing. Nitroform starting material may, if necessary. be pre- pared by the alkaline-peroxide reduction of tetranitromethane, and fluorinated &; in this case, yields of I11 from 65 to 7 6 (based on tetranitromethane) are obtained. The route shown in (4) was discovered by workers at the U,S. Naval Ordnance Laboratory and substantial improvements since then, primarily by NOL, have made the process a very attractive one. The reduction of 111, when carried out at -5 to -1OOC in alkaline medium with a 20$ excess of hydrogen peroxide and formaldehyde, gives yields of 90$ FDNE in 95 mole-percent purity. The reaction can be effected in aqueous methanol in order to enhance the solubility of FM in the reaction mixture, or, alternatively, a surface-active agent such as sodium ptolunesulfonate or Triton X-lOO+, may be added to achieve the 'same result. The latter method is particularly advantageous when it is desired to use the solution of FDNE in the methylene h alkyl phenoxy polyethoxyethanol (Rob & Baas CO.) (4) 3
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Introduction<br />
56.<br />
FLUORODINITROETUNOL AND DERIVATIVGS"<br />
Henry J. Marcus<br />
Aerojet-Ceneral Corporation, Azusa, California<br />
The chemistry of 2-fluor0-2,2-dinitroethanol has been investigated for tho past<br />
several years, <strong>and</strong> it is a privilege to present some of this material at thia time.<br />
This paper presents a 31.1nmary of a process evaluation study, <strong>and</strong> much of the chemistry<br />
involved will be reported in greater detail by the original authors in the coming<br />
months. It may be stated at the outset that the chemistry of fluorodinitromethyl<br />
,compounds shows marked similarity to trinitromethyl or e-dinitromethyl compounds,<br />
which are well-known in the literatureo<br />
Synthesis of 2-Fluoro-2.2-dinitroethanol .<br />
One preparative method for 2-fluoro-2,2-dinitroethanol (FDNE) is based on tho<br />
fluorination of the aci-sodium <strong>salt</strong> of dinitroethanol<br />
NO,@Na@<br />
n L :02<br />
F2(or C103F) + C - CH20H FC CH20H<br />
I<br />
N02<br />
The starting material fcr Reaction (1) is prepared in situ by the deformylation of<br />
2,2-dinitro-l,Fpropanediol <strong>with</strong> one mole of base<br />
NO2<br />
y 2 N02%a@ n<br />
+ NaOH C CH20H<br />
11<br />
Compound I1 is preferably prepared by the oxidative nitration of Z-nitro-l,Fpropanediol<br />
(Reference 1). I1 is not isolated, but is partially purified by extraction<br />
from the aqueous reaction mixture <strong>with</strong> ethyl or isopropyl ether, followed by an extraction<br />
of the ether solution <strong>with</strong> aqueoue base, which converts I1 to the aci-sodium<br />
ealt of dinitroethanol. Although other methods of preparation of I1 are known, tho<br />
route shown was the one of choice.<br />
Conversion of I1 to FDNE was carried out by introducing fluorine gas, diluted<br />
1:l <strong>with</strong> nitrogen, into the ahueoue solution of the aci-sodium <strong>salt</strong> at 15 to 25O<br />
(Reference 2). It was found that efficient dispersion of the fluorine is eseential,<br />
<strong>and</strong> that stainlesa steel gas-inlet tubes <strong>with</strong> open ends of 1/4 or 3/8 in., or <strong>with</strong><br />
various hole aizee of 0.016 to 0.040, are eatisfactory in a 50-liter vessel. Th<br />
amaller the diameter of the holes, however, the more frequently were they occluded<br />
by soaim fluoride.<br />
I<br />
N02<br />
A rapid injection of water served to remove the obstruction.<br />
This report ie based on work supported, in large part, by the AEC through the<br />
Lawrence Radiation Laboratory of the University of California.
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