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
60. identified (Reference 7) as the FEFO analogs with two and three methy’leneoxy chafns in the molecule, respectively. V VI Compounds V and VI seem to arise whenever the condensation medium is contaminated with water. If one is aware of this beforehand, the problem can be overcome by the use of fuming sulfuric acid, as shown i n Table 2. TABLE 2 , EFFECT OF DILUTION WITH WATER ON FEFO SYNTHESIS ~o10-s Components Case No. Condi tions with lower CC retention time $ FEFO $ *ah-boilers $ Yield - 5 Standard* 3.6 93.4 3-0 92.5 6 IO$ H20 added to PDNE 4.3 44.7 51.0 83.6 7 As in 93, with 20-29 2.9 93.4 3.7 77.7 fuming &SO4 in place of conc. H SO 2 4 2.0 moles of FDNE (distilled) per mole of formaldehyde Results similar to those of Case No. 6 are obtained whenever the FDNE-methylene chlorido solutions are inadequately dried. If the FEFO product is still too highly Contaminated with V and/or VI, purifica- tion may be effected by low-temperature crystallization from methylene chloridchexane in a tedious, somewhat wasteful procedure, or by agitation with concentrated sulfuric acid. Result5 from the latter treatment are presented in Table 3. m TABLE 3 PURIFICATION OF FEFO WITH SULFURIC ACID , Case No. 8, crude #ole-% Components with lower CC retention time $ FEFO 1.2 87.3 $ Eiph-Boilers -- v VI $ Recovery 5.6 5.9 - 8, purified 9, crude 9, purified 1.7 0.7 1-4 96.6 95.6 98-6 0.1 3.7 - 1.6 - 82 - - 89 I1 Extremely interesting results were obtained in the course of preparing FEFO from an FDNE-methylene chloride solution after attempted purification. This FDNE was prepared fro= f luorotrinitromethans in aethanolic solution. and the FDmmethylene chloride solution was later found to be highly contaminated with methanol and water. The crude FEFSmethylene chloride solution, following separation from the sulfuric acid layer, was divided into two equal portions. One portion was worked up in tho usual manner, and the other waa treated with two portions of concentrated sulfuric 1 4 i i L
I I \ 61. acid before being worked up. The first portipn gave a yield of 48 percent (calculated as FEFO), the second 42 percent. GC analysis showed the following results: TABLE 4 IN-PE1OCESS PURIFICATION OF FEFO WITH SXJLFURIC ACID Case No. Mole-$ Components with lower GC retention time i'. FEFO $ Hiph-Boilers V VI 10, treated as usual 17.1 37.6 43.8 1.5 10, purified in process 1.0 93.7 503 In spite of the fact that the conventionally-treated FEFO was apparently not completely freed of solvents, and the results are thus not strictly comparable. it is evi- ,d-nt that a very high degree of purification was achieved. Since the yield of FEE'O was nearly the same in both cases, it must be concluded that purification took place primarily other than through extraction of V and VI, and that the latter may have been converted into FEFO by a process indicated in the following sequence: H 8 XOCH20CH20R + H @ ROCH20 CH20R (6) IL '[ROCH2] 8 + ROB (RO)~CH~ + H@ 8 I' bCH2] + HOCH20R e ROH + HCHO The purification of 'FDO with concentrated sulfuric acid immediately following separa- tion of the FEFO-methylene chloride solution from the sulfuric acid reaction medium has consistently removed nearly all of the high-boiling contaminants, and has been made a standard procedure in FEFO preparation. Several routes are known which yield FEFO from intermediates other than FDNE. One of these methods utilizes &(2,2,2-trinitroethoxy) methane (VXI) as the starting material (Reference 4) - , > [(N02)3CH20]2 CH2 [(N02)2C %H20]2CH2 7 FEFO (7) H202, OH . D ' VI1 VI11 VI1 is reduced to the disodium salt (VIII) in the presence of alkaline peroxide in aqueous methanol. The organic solvent, added initially to ensure solubility and facilitate reaction of the starting material, must then be removed by vacuum distillation prior to fluorination. The product has been obtained in yields of up to 60$ by this route. The sensitivity of VII, and the fact that large volumes and much time are re- quired to effect the removal of the methanol, are severe disadvantages in this process. Moderate yields of pure FEFO ore obtained via another route which utilizes VI1 as the starting material: The conversion of VIII, by means of the Henry reaction, to bis(Fhydrory-2,2-dinitro- propoxy)methane serves as a means of purification, and as a result the yields from IX -
- Page 9 and 10: 1 3 9 SOYO FILLER,HQT PRESS Fig. 4.
- Page 11 and 12: 11. COAL PYROLYSIS USING LASER IRRA
- Page 13 and 14: 13. Macerals. Macerals from a singl
- Page 15 and 16: i 1 I Photochemistry. A fundamental
- Page 17 and 18: t P li. al ’ i ._ m LL
- Page 19 and 20: ' 19. PYROLYSIS OF COAL IN A MICROW
- Page 21 and 22: I 21. In the third stage, the gas e
- Page 23 and 24: .4 4 0 W 0 m .d m x .-( 0 x w M m s
- Page 25 and 26: ' 25. CONCLUSIONS The principal rea
- Page 28 and 29: ' .4 b s tract 28.
- Page 30 and 31: 30. the course of the experiment Ex
- Page 32 and 33: d (Sulfur] dt m i trogenj dt 32. E
- Page 34 and 35: 34. Table 1, Properties of Feed Mat
- Page 36 and 37: 0 0 0 m 0 VI b N 0 c, VI N 0 v, N h
- Page 38 and 39: - Literature Cited 38 1. Gordon, K
- Page 40 and 41: 40 z - B 30 w 6 20 yl w U 10 40. 10
- Page 42 and 43: Z 0 In 80 CK W > 6 60- 0 I- 40- Z W
- Page 44 and 45: 44. 2.0 I 1.2 - 0 2 1.0- 0.8 i TIME
- Page 46 and 47: - 2.81 1.NITROGEN 2. SULFUR 3. GASO
- Page 48 and 49: 48. The oil from the separator is v
- Page 50 and 51: . 50 . Table I . Properties of Pitc
- Page 52 and 53: 52. Coke yield A - - - - 0 800 900
- Page 54 and 55: FIGURE 8. 54. t 0.5 1 800 900 1,000
- Page 56 and 57: Introduction 56. FLUORODINITROETUNO
- Page 58 and 59: chloride extractant without other h
- Page 62 and 63: 62. to FEFO -e quite high (80 to 85
- Page 64 and 65: 64. RECENT CHEMISTRY OF THE OXYGEN
- Page 66 and 67: polymers for the conventional fuel
- Page 68 and 69: 68. In summary, two general methods
- Page 70 and 71: 70. Table XI1 Differential Thermal
- Page 72 and 73: vapor Pressure (psia) Figure 4. Vap
- Page 74 and 75: C H -0-C-NHF, - 2 5 II 0 74. H 9304
- Page 76 and 77: 76. The infrared spectrum is descri
- Page 78 and 79: , 78. PREPARATION AND POLYMERIZATIO
- Page 80 and 81: . .- . - ..... . . I ,caving the re
- Page 82 and 83: If it ~ 3 ~ o~t 7 s Y'2t the therm1
- Page 84 and 85: Chlorine Fentafluaride T q D OC 252
- Page 86 and 87: , 86. Zeections of Cl30 and AsF5. M
- Page 88 and 89: aa . - The rrost difficult rctionel
- Page 90 and 91: 90. DENSITY, VISCOSITY AND SURFACE
- Page 92 and 93: 92. If it is assumed that the syste
- Page 94 and 95: 94. After condensation of oxidizer
- Page 96 and 97: Stirring Solenoid LHe 7. Cryostat 9
- Page 98 and 99: Introduction 98. RFACTIONS OF OxYcm
- Page 100 and 101: , Acknowledgement 100. This work wa
- Page 102 and 103: 102. volume and then by pumping to
- Page 104 and 105: 104. The x-ray powder pattern (Tabl
- Page 106 and 107: Irredie tion Time, mi&) 106. Table
- Page 108 and 109: I. Introduction 108. RE7IIEw OF ADV
I<br />
I<br />
\<br />
61.<br />
acid before being worked up. The first portipn gave a yield of 48 percent (calculated<br />
as FEFO), the second 42 percent. GC analysis showed the following results:<br />
TABLE 4<br />
IN-PE1OCESS PURIFICATION OF FEFO WITH SXJLFURIC ACID<br />
Case No.<br />
Mole-$ Components<br />
<strong>with</strong> lower GC<br />
retention time i'. FEFO<br />
$ Hiph-Boilers<br />
V VI<br />
10, treated as usual 17.1 37.6 43.8 1.5<br />
10, purified in process 1.0 93.7 503<br />
In spite of the fact that the conventionally-treated FEFO was apparently not completely<br />
freed of solvents, <strong>and</strong> the results are thus not strictly comparable. it is evi-<br />
,d-nt that a very high degree of purification was achieved. Since the yield of FEE'O<br />
was nearly the same in both cases, it must be concluded that purification took place<br />
primarily other than through extraction of V <strong>and</strong> VI, <strong>and</strong> that the latter may have been<br />
converted into FEFO by a process indicated in the following sequence:<br />
H<br />
8<br />
XOCH20CH20R + H @<br />
ROCH20 CH20R<br />
(6)<br />
IL<br />
'[ROCH2] 8 + ROB (RO)~CH~ + H@<br />
8 I'<br />
bCH2] + HOCH20R e ROH + HCHO<br />
The purification of 'FDO <strong>with</strong> concentrated sulfuric acid immediately following separa-<br />
tion of the FEFO-methylene chloride solution from the sulfuric acid reaction medium has<br />
consistently removed nearly all of the high-boiling contaminants, <strong>and</strong> has been made a<br />
st<strong>and</strong>ard procedure in FEFO preparation.<br />
Several routes are known which yield FEFO from intermediates other than FDNE.<br />
One of these methods utilizes &(2,2,2-trinitroethoxy) methane (VXI) as the starting<br />
material (Reference 4)<br />
- ,<br />
> [(N02)3CH20]2 CH2 [(N02)2C %H20]2CH2 7 FEFO<br />
(7)<br />
H202, OH .<br />
D<br />
' VI1<br />
VI11<br />
VI1 is reduced to the disodium <strong>salt</strong> (VIII) in the presence of alkaline peroxide in<br />
aqueous methanol. The organic solvent, added initially to ensure solubility <strong>and</strong> facilitate<br />
reaction of the starting material, must then be removed by vacuum distillation<br />
prior to fluorination.<br />
The product has been obtained in yields of up to 60$ by this<br />
route. The sensitivity of VII, <strong>and</strong> the fact that large volumes <strong>and</strong> much time are re-<br />
quired to effect the removal of the methanol, are severe disadvantages in this process.<br />
Moderate yields of pure FEFO ore obtained via another route which utilizes VI1<br />
as the starting material:<br />
The conversion of VIII, by means of the Henry reaction, to bis(Fhydrory-2,2-dinitro-<br />
propoxy)methane serves as a means of purification, <strong>and</strong> as a result the yields from IX<br />
-
Change language