Products and the synthesis of chloronitrobenzol with certain phenolates are discussed, as is the p-oxyphenylether occasionally produced. Yield, melting point, and physical description are given for each product. The products include 2,4'-dinitrophenylether; 2,2'-dinitrophenylether; p-nitrophenylether-p-oxybenzoic acid and its methylester; p-aminophenylether-p-oxybenzoic acid, its sulfate, and its barium salt; and p-oxypenylether

Bauer, E.

Haeussermann, C.

English

NASA Technical Reports Server

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NII-!JI TILI- 77 tJ d-.-tJ 
NASA TECHNICAL MEMORANDUH NASA TM-77020 
ON SOME DERIVATIVES OF PHENYLETHERS 
II. REPORT 
" C. Haussermann and E. Bauer 
NASA-TM-77020 19830016284 
" Translation of "Uber einige Abkommlinge des Phenylgthers," 
Berichte Deutsche Chemischen Gesellschaft, Vol. 29, 1896, 
pp. 2083-2085. 
" n n rJ n iJ:r Ii' ~ n ~ 7 L b U :H1 L i\ d lJ IJ:-- u 
FEB 1 61983 
LANGLEY RESEARCH CENTER 
LIBRARY, NASA 
HM.~PTON, VIRGINIA 
NATIONAL AERONAUTICS AND SPACE ADMINISTRATION 
lmSHINGTON, D.C. 20546 JANUARY 1983 
I 111111111111111111111111111111111111111111111 
I NF00292 
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STANDARD TITLE PAGE 
1. R.por. No. 2. Governmen. Acc ... ion No, l! Reclpien". Cololog tlo • 
. ' NASA TM-77020 
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~, Till. ond Sublili. 5, Repo;, Dol. 
ON SOME DERIVATIVES OF PHEN~LETHERS ,TANUARY 1983 
II. REPORT 6. p.rrorming Orgonizolion Code 
7, Au.hQr(d 8. P.rlorming Organi zotion Repor' No. 
C. Hi{USSERMANN and. E. J3AUER 
10, Work Unit No. 
~. P,rEorming Orgoni zal,on Neme end Address 11. Conlract or Gront No. 
LEO' KANNER ASSOCIATES NASw-354l 
REDWOOD CITY, CA 94063 13. Type o' Repor. and Period Cover." 
Translation 
12. Sponsoring Agency Nom. and Addre .. 
NATIONAL AERONAUTICS AND SPACE ADMINIS-
TRATION, ~vASHINGTON , D.C. 20546 I.e. Sponaorln:! Agency Code 
15. Supplemen.ary Notes 
" " " Translation o;f "Uber'einige.Abkommlinge des Phenylathers, " 
Berichte Deutsche Chemischen Gesellschaft, Vol. 29, 1896, 
pp. 2083::-2085. 
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16. Abslroct 
Products and their synthesis of chloronitrobenzol with certain 
phenolates are discussed, as is the p-oxyphenylether. occasional ly 
produced. Yield, melting point, and phys~cal description are 
given for each product. The products include 2 4'-, . 
dinitroph~nyletheri'2;2'-dinitrophenyl~ther; p-nitrophenylether 
p-oxybenzoic acid and its methylester; p-aminophenylether-p- I 
oxybenzo·ic acid, its: sulfate, and its'barium salt; and p- i 
oxyphenyle:ther. I 
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ON SOHE DERIVATIVES OF PHENYLETHERS 
II. REPORT 
C. H~ussermann and E. Bauer 
Chemical-Technological Laboratory of the Technische Hochschule, 
Stuttgart 
The behavior of chloronitrobenzol with certain phenolates /2083* 
outlined in an earlier paperl has been studied by us in the meantime, 
and in what follows we shall describe the products obtained as well 
as the p-oxyphenylether occasionally produced. 
2,4'-Dinitrophenylether 
To produce this compound, the strongly colored reaction product 
formed at 140° between p-chloronitrobenzol and o-nitrophenol 
potassium is treated with steam, then vacuum distilled. The 
distillate is repeatedly crystallized in glacial acetic acid and 
then finally in alcohol. 
Analysis: calculated for ClzHaNzOs. 
percentages: C 55.38, H 3.08, N 10.80. 
found II " " 55.39, " 3.20, " 11.05. 
The 2,4'-dinitrophenylether forms long, white needles which 
melt at 103.5° and dissolve in approximately 210 times their weight 
of alcohol at 17.5° or in 5.5 times their weight of boiling alcohol.2 
If the ether is treated in alcoholic solution with tin and 
hydrochloric acid, then ~t is transformed to a chlorohydrate (found: 
Cl 25.4% calculated for (C6H4N "2)20 • 2 HCl 26.0%)), from whose 
aqueous solution a base with a melting point of 78-80° can be 
*Numbers in the margin indicate pagination in the foreign text. 
IThis publication, Vol. 29, p. 1446. 
2We could not isolate this dinitrophenylether from the product pro-
duced by the action of concentrated nitric acid on phenylether; 
whereas it was easy to separate the previously described isomer with 
melting point 143.5°, in pure form. 
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precipitated with ammonia. 
2,2'-Dinitrophenylether 
The preparation attained by analogous means from 0-
chloronitrobenzol and o-nitrophenol potassium forms dull, white 
needles, when crystallized from alcohol, that melt at 114.5°. 
Analysis: found percentages: C 55.02, Ii 3.10, N 11.05· 
One part of the substance requires approximately 150 parts 
alcohol at 20° or 3.8 parts boiling alcohol to dissolve it. 
Reduction in acid solution produces a diamine which we are still 
investigating. 
p-Nitrophenylether-p-Oxybenzoic Acid 
/2084 
This compound is obtained by adding dipotassium-p-oxybenzoate 3 
\ at 160°, with constant stirring, to a large quantity of p-chloro-
nitrobenzol. The temperature is then gradually raised and finally 
kept at 235° for approximately 6 hours. The melt is then dissolved 
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in dilute sodium hydroxide solution, the unreacted chloronitro-
benzol is filtered off, and the filtrate is mixed with hydrocloric 
acid. The ether acid thus precipitated is siphoned off, washed, and 
after drying, recrystallized in simmering alcohol, after which it 
is obtained in the form of small colorless prisms. 
Analysis: found for C13H9N 05. 
percentages: C 60.23, H 3.48, N 5.41. 
found " " " 60.40, " 3.71, " 5.7. 
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.The p-ni trophenylether-p-oxybenzoic acid N'()2Cr. II ,()('r.II,COUII, 
melts at 236-237°. It is insoluble in water and only slightly 
3The dipotassium salt of p-oxybenzoic acid is produced by introducing 
a hot, absolute alcohol solution of 1 Mol of the acid in a similar 
2 Mol solution potassium alcoholate, siphoning out the precipitated 
salt and drying it over a water bath. 
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soluble in hot alcohol, ether, and chloroform. 
The barium salt obtained from the free acid and barium 
carbonate (calculated: Ba 20.98%; found: 20.79%) crystallizes 
from a hot aqueous solution in a nonhydrated state. 
The methylester (calculated: N 5.2%; found: 5.2%) is obtained 
by treating the acid with alcohol and hydrogen chloride in a 
waterbath and precipitating the product by adding water, then 
recrystallizing the precipitate in alcohol. This process yields 
matted needles that melt at 108-109° and are easily soluble in 
benzol. 
p-Aminophenylether-p-Oxybenzoic Acid 
The nitro acid is warmed for some time in a water bath with 
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tin and hydrochloric acid with the addition of some alcohol. The 
\ fluid is then diluted and freed of alcohol by heating, freed of 
tin with hydrogen sulfide, and finally concentrated by filtration 
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and cooled to yield a poorly soluble chlorohydrate. Acetic acid /2085 
precipitates the free amido acid from the alkali solution of the 
chlorohydrate, which, after recrystallization in alcohol, yields 
yellowish-white, atmospherically stable platelets. 
Analysis: calculated for C13HIIN03. 
percentages: C 68.12, H 4.8, N 6.11. 
found " " " 67.91, " 5.0, " 6.50. 
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The p-aminophenylether-p-oxybenzoic acid NlhC6IJ j OCr.IJtCOOfI 
melts at 193-194°. It is only slightly soluble in water and more 
soluble in alcohol and chloroform. The chlorohydrate (Cl calculated 
for (C6H4)20 . eOOH . NH2 • HCl 13.37%; found: 13.21%) forms weakly 
gray scales, slightly soluble in cold water. 
The sulfate (H2S04 calculated for [(C6H4)20 . COOH . NH2]2H2S04 
" 17.62%; found: 17.78%) consists of a crystalline powder which 
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dissolves only with difficulty in cold water. 
The barium salt produced fron the free acid and the barium 
carbonate (Ba calculated for [(C6H4}20 • NH2COO]2Ba 23.1%; found: 
22.9%) is easily soluble in warm water and crystallizes therefrom 
in the form of white needles, while the very easily soluble sodium 
salt forms silky crystals. 
with the usual azo-compounds, such as resorcinol, salicylic 
acid, naphthol- and naphthylaminsulfonic acids, the acid yields, 
after diazotizing, yellow to red dyes which are taken up by wool 
in an acid bath. 
p-Oxyphenylether 
The conversion of the p-aninophenylether into the corresponding 
phenol is easily accomplished, even if not without some loss, by 
means of boiling with excess amounts of hydrochloric acid and the 
'\ calculated amount of nitrite containing solution. The raw phenol 
which separates in the form of a black oil is purified by vacuum 
distillation and subsequent recrystallization from a mixture of 
equal volumes of benzol and petrolbenzin. Finally, the product 
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is dissolved in hot water from which it precipitates after cooling 
in the form of very fine, white, matted needles. 
Analysis: calculated for C12HI002. 
percentages: C 77.42, H 5.38. 
found " " " 77.28, " 5.60. 
The p-oxyphenylether melts at 84-85° and is easily soluble in 
the ordinary solvents with the exception of water in which it 
dissolves only with difficulty at room temperature. The cold 
aqueous solution is not colored by iron chloride. 
with diazobenzolchloride, the alkaline solution yields a 
brown-red dye. 
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End of Document 


On some derivatives of phenylethers, 2

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