2.NITRO- 1, 3..INDNDIQNE
AND ITS USE AS A REAGENT POR
TRE IDENTIFICATION OF ORGANIC BASES
by
submitted to
in partial iu]iiUmeut o
the requirements or the
degree oZ
MASTER OP SCIENCE
June 1947
Redacted for Privacy
Redacted for Privacy
Redacted for Privacy
Redacted for Privacy
cria*ne,
TABLE OP CONTENTS
......,.... 1
GeneralDisoussion......
Table 1. The yield of 2-nitro-1,3-indandione
secured from 2 grams of 1,3-indandione under
various conditions.
Rxperimental
.
*
. .
.
. .
*
. . .
. .4
.
, . . . . . . . . . . . . . .
. .
6
alipbatioamines..........,,....8
Table 2. The 2-nitro-1,3-indandionates of the
Table 3. The 2'nitro-1,3-indand.1onates of the
aromatic amines
. .
. . . . . . .
. .
. .
*
. . 10
Table 4. The 2-nitro1, 3-indandionates of the
heterocyolicamines.
.
*
. ... .
.
.
.
.
.
.13
DiscussionofResults...............
Bib1iophy .
.
.
.
*
.
.
.
.
.
.
.
a
.
a
.
.
.
15
.
17
2'.NiTRO-1,3INDANDIONE AND ITS USE AS A RBAGT
POR THE IDENTIFICATION OP ORGANIC A8ES
The mo8t uaeful type derivative of primary and secondary axnines are the amides, phenyithioureas, and sulfon-
amides; and of the tertiary amines, the picrates and the
quaternary ammonia salts,
Bensene sultonyl chloride is
probably the most frequently used reagent since it is
employed in both the preparation of these derivatives and
in the usual procedure (Hinaberg's method) for classifying
Amines.
In 1936, G. Wanag (3,4) reported a new reagent,
2-nitro-1,3-indandione, which forms salts with both the
inorganic and organic cations, suoh as the simple aliphatic,
aromatic, and heterocyolic wnines.
He found these com-
pounds to be crystalline, non-hygrosoopic, shaz-melttug salts that were very soluble in water.
Later invest.
tigatora at Wanag' a suggestion used this strong acid to
prepare certain derivatives of the alkaloids (2) and
amino acids (1).
The fact that many of these salts hydrolyze to
such an extent in water that a neutralization eqyivslant may be determined by standard procedures was not
realized by Wanag.
This property, coupled with its
ease of salt formation, uon-byGxosoopic character, and
sharp-melting point range makes it appear to be an
unusually promising reagent for the identification of
orrnic bases.
Although neutralization equivalents
may also be oh tamed with the hyirochlorides of' the
bases, these, sales are for the most part hyGroscoic
and therefore totally unsuL table for equivalent
eight
determthatlori.
The salts were orinally repsred by alcLLng an
aqueous solution of the acid to a dilute hydrochloric
acid solution of the base,
However, as 2-nitro-1,3
indandione itself' is very irsoluble in dilute hyrochloric
acid, imoure salts were obLaied that hau to be recrystallized sev;ral times.
Since the precipitation proce-
dures were not unif'ori, and orouucts in'pure, a study of
the salt fornaatiori in vsrious solvents was undertaken.
In the course of this work it was discovered that very
pure salts of 2-nitro-1,indandione could be orecipitatod
from acetone solution of the base or its hydrochloride.
2-Nitro-i,3-indandione was first nrepared () by
the direct nitration of l,-indandione with cold fuming
nitric acid in glacial actic acid.
hanag, reortiog
yields of' 78, found that the conditions for this re-
action vero very c itical since the temperature at which
nitration takes
the same.
lace and oxidation occurs is nearly
The critical conditions were eonfired in this
labor:tory; but the yields were uncertain and were never
greater than 64.
i3eeause of the uncertanties of this
reaction :anag also attempted to prepare it by oxidizing
2-nitroso-1, 3-indanuione with concentrated nitric acid
and by condensing sodium nitrite with 1, 3-inuandione
at 800 - 900 C. (6) to give tho sodium salt of 2-niro-
l,5-indandione.
In ecch istsnce the yields
re low.
In view of the poor or erratic results using fuming
nitric ada and the promise of 2-nitro-1,3indandione
as an organic reagent a further seudy of the direct
nitration of l,--indandiono was made.
Concentrated
nitric acid was used as the nitrating ageat in place of
fuming nitric acid since initial work indicated a greater
difference between the nitration and oxidation temperatures. Table 1 summarized the results obtained upon the
nitration of two grams of 1,3-Indandiane under various
conditions. Incomolete nitration takes olace if the
mixture is not heated to at least 450 C., or if the
nitric acid concentration Is diminished. If the mix-
ture Is heated over 50 C. but under 730 C. a large
amount of a yellow by-product ;ieIting at j350 c results.
Complete oxiu.atioii to pLthalIc acid occurs i1 the rLitration is allowed to roceed at emeratures above 80°
C.
Partial oxidation also occurs if the nitric acid
content is increased. The light yellow precipitate of
2-nitro-1,3-indandione hydrate must be filtered rapidly
and ithout agitation, as proLonged contact with the
4
Table 1
The yield of 2-nitro-1,3-indandione securea from
two Rrans of 1, 3-indaine under various conditions.
Temperattire
30
40
48
56
60
40
40
40
40
40
40
40
40
Time
cooling
minutes
60
30
60
60
60
60
30
90
120
60
60
60
60
60
Acetic
Nitric
ml.
ml,
acid
20
20
20
20
20
20
20
20
20
15
10
25
30
20
yield
c1d
2
2
2
2
2
2
2
2
2
2
2
2
2
3
did not nitrate
76
84
70 some oxidation
25
traces
76
78
57
75
23
79
62
38
5
nitrating iixture causes a cor
Neither can
he
sondin, loss in yield.
recipit5te be filtered too soon as
uf-
ficient tI.e nust be allowea for the precipitate to forr.
l,3-inoandioeiray also be nItrtet with soaiu
nitrate
rlacial acetic acid at 1000_1050 c., or.with nitrogen
tetroxide In obloroforc.; but as the yields vre poor
these latber .ethods were abandoned.
2-Nitro-1,3-indanaione can be 'eadily bro'inated
(s) or chlorinated. (5) to fori the 2-halo-2-nitro-1,3indandione.
However, it can be neither nitrated, nitro-
sted, benzoylated, or acetyla
d.
It decoposed up3ri
oxidation or upon the action of concentrated base or acid.
to fri phtbaiic acid or
Since the
hthalic anhyuride.
ormu1a In Figure 1 cannot satisfactori.Ly
explain the acidic chaxcter of 2-nitro-1,3-indandione,
0
c/sc
II
I
I
,°
OH
NV
Fiure 1
Finire 2
Ehioi- form
Keto-- form
0
ciç
°r"II
I
0
I
Figure 3
Keto-nitric acid form
two aduitional structures have been proposed (u).
dow-
ever there appears to be no direct evidence to substantiate
either the enul-fora (Figu'e 2) or the keo-nitric acid
for.n (Figure 6).
2-NITR0l,3-IbNi.IOL.:
Twenty grams of 1,3-indan-
diono and 200 milliliters of r1acial acetic acid
are
warmed in an ir1enoeyer flask on a water bath to about
480
0,
To this is added in a siie aniouiith constant
aitatiof1 twenty miililters of concentrated nitric
acid (st. g. 1.42). After about five seconds he reaction oixture, which darkens considerably, is cooled
rapidly with. runriin wster or in an ice bath to 100 C.
After one hour at t is tern erature the yellow preciitate
of 2-nitro-1,3-indandiorio is removea by suction filtration and is washed ith a little cold acetic ada. The
yield aftei recrystwlization from a little water is
rams (77-84) of the yellow hydrate, contdnin
one mole of rater ana elti at 1130 C. Upon dryinp, in
a vacuum desiccator over sulfuric acid all the water of
22-24
crystallization is lost, end the 2-nitro-1,3-indanaione
is transformed into an intense yellow, anhydrous oowder,
whici cannot be recrystallized from an anhydrous solvent.
If the nitratimp; mixture is poured into water after
rernovinn the 2-nitro-1,3-indanuio;e a yellow comound
that melts at
C. and contains 5,19 nitrogen is
secured. As the c000und could not be kept in the
crysailic bate notbig fuxther as uone Wit lb.
1350
7
SALTS OF 2-NITRO-1,3-ThDANDIONE:
To a solution
of the organic nitrogen base or base hydrochloride in
acetone is added a slight excess of a saturated solution ol 2-nitro-1,3-indandione.
(The solution is pre-
pared by adding five grams of the acid to 150 ml. ol'
acetone.
The solubility of 2-nitro-1,3-indidione in
acetone is 0.025 g./ml. at 18° 0,; and 0.032 g./ml. at
24° C.)
If the precipitate does not foxm immediately
the solution is evaporated at room temperature to about
one-half of its original volume.
The salts are recrys-
tallized from 95% ethyl alcohol, water, or a combination
of both.
The salts thus prepared are very pure and melt
within a range of one degree.
A list of the salts prepared with their corrected
melting points, analysis, and solubility in various
solvents is to be found in Tables 2, 3, and 4.
The salts
formed from bases which were so strong as not to permit
the determination of neutralization equivalents are
marked N.T. (not titratable) in the table.
The values
which are reported agree within 2% of the theory.
Table 2
The 2-nitro-1,3-inc&aridionbs of the
a11;:hz.tic
amine a,
the 2-nitro-1,3-inctandionate of
m.p.
00. N.E.
: N
caic. found
soub10 in
-
Si pie:
Methyl aniine (4)
thy1 amine (4)
n-Propyl amine (41
io-Propy1 amine
nr3utyi amine
iso-Butyl amine (4)
i-Amy1 amLne
iso-Amyl amine
isc-Hexy1 amine
.
205
203
185
205
147
N T.
M m
J.
'.
N T.
1 7
158
162
155
ri-Heptyl amine (4)
150
n_Heoty1cteer1 aniae (4)110
Allyl amine (4)
181
Cyclohexyl amine (4)
213
Camphy]. amine (4)
1o9
Bornyl amine (4)
211
thylenedi amine
222
Ethy1enedia'ine (4)
205
Propyl enecii am Inc
206
Putrescine (1)
Cadaverine (1)
£)i-net,hr1 amine (4)
210
Di-ethyl amine (4)
1'1
Di-proy1 amine (4)
210
ui-isoproy1 amLe
237
Di-n-butyl amine
204
Di-iso-butyl amine (4) 231
Di-sec.-buty1 amine
234
Di-n-Amyl amine
137
Di-isoamyl amine (4)
190
Di-n-hexyl amine
117
Di-isohexyl amine
133
D.-cyc1ohtxy1 amine
235
Di-n-h.eotyl amine
107
Di-n-octyl aine
91
D1-F-ethy1-hexy1 amine 144
Di-n-noyi amine
83
Di-n-decyl ai.e
Sb
Tri-meehyl
(4)
162
.Tri-t:'j1 a.ie(4)
oil
ri-isohuty1 avIno (4) lii
j.. A..
1. 2.
N. T.
12.54 12.84
11.89 11.40
11.2 11.O
11.22
10.62
10.b2
10.07
10.07
9.59
9.17
11.30
10.64
10.
9a73
10.24
9.2,
9.28
o.
.. I.
11.32 11.00
10.00 9.68
8.43 8.22
8.14 7.60
13.08 13.06
12.67 1.80
j\ 2.
A-;.
N T.
_4 S
'K
i-' £
:
£
fl
1',. Le
1T
'1
. a..
1e A
I.
. L,
12.28 12.03
11,92 12.03
11,57 11.20
11.
11.20
10,ol 10.83
9.5? 9.85
9.59
8.75
8.75
3,75
8,05
8.05
7.45
7.45
7.45
6.92
6.50
o.50
'.09
9.61
8.79
9.10
8.81
8.00
8.05
7.40
7.32
7,48
7.01
6,61
6.44
6.11
5.81
5.73
11.20 11.40
8,91 t.-5
rj
isz
(d
i
c,
:
1.j
'J
4.J
*
* *
* * *
**
*
* * * *
* *
*
**
* * * *
*
*
*
*
*
*
*
*
*
*
*
*
*
*
*
* *
* *
*
* *
*
* * *
.:? * *
* * *
* ***
Table 2 continued
The 2-nitro-1, 3-in,iandionats o
the au
hat1 c
arni ne a.
the 2-nitro-1,3-inthm- m.t.
OÔ N..
dionate of
N
caic. found
soluble in
- tU
S.)
Alcohol:
187
Ethanol aiiine
13:
Triethanol amine
2,3-Die nlno-1-pronanell95
N.T.
N. 11.
N. ie
Hydro xye thyl ethylene-
184
dinuine
2, 3-Dihydroxy-l-oro2yl
176
amine
2, (2_aino ethoxy)
ethanol
119
11.16 11.11
8.23 8.13
11.86 11.69
*
* *
11.51 11.43
*
*
N. 2.
9.93
9.97
4'
N. 1.
9.46
9.31
*
Acid:
Glyclne (1)
b-Alanine (1)
Arni de:
Guanidine (4)
256
240
Urea
Phenyl urea
163
140
AcetaNiladiNe (4)
Arrinine (1)
Wethyl uaridine (1)
Inidazoyl:
Histamine (1)
His tidine (1)
Carnosine (1)
251
32
22.41 22.30
16.87 16.84.
* *
*
16.73 16.24
12.84 12.87
* *
* * *
10
Table 3
The 2-nitro-1,3-inua
es of the ar.atio
ion
a 1nes.
the 2-nitro-1,3-inancilonste of
rn,p.
"C.
N..
N
caic. found
so1b1e in
--
-
-L
Simple:
Aniline (5)
o-Toluiciine (3)
m-Toluidirxe (3)
9-TOluidifle (3)
209
198
194
193
192
Xylidine 1,s,4 (4)
185
1,3,2
(4)
Xy1idir
196
Xy'id1e 1,4,2 (4)
216
Xylidine 1,3,5 (4)
1 0
Benzyl azine (4)
a-Phenyl ethyl a!ii1e(4)207
b-Pienl ethyl
2u
.rnine(4)169
Benzedrine
Benz xyiry1 amine (4)
o-Ethyl aniline (4)
p-thii antlise (4)
o-i1LobLntny1 (4)
n-Ainobiheri1 ()
p-AnLnohiphezyJ. (3)
a-Naphthjlaine (4)
b-Nao}tthy1ai:t (4)
193
205
183
i:1
163
19
190
210
193
Le r ah j-iro - a-na itthl
204
azzLne-ar ()
Te.tralyro-b-ria;hthyi
a.tie-ac (
o-Phenr ieri a;.iie ( 4 ) 174
m-Phen-leniaAne (4) 200
p-Phenylendiine (4) 263
)
To1iyleeJiaue-1, 2,4
183
195
2, 7-iJianino flroene( 4)240
213
Benziuine (4)
216
o-T,lldine (4)
203
iibenziaiLie (4)
(4)
2-Amno I'lorerie (4)
N-Izobut7l benzyl amine220
N-ne ebvi aniline (0)
106
328
9.86
9.40
9.40
9.40
8.98
8.98
8.98
o.90
6.39
8,97
8.97
8.59
7.52
8,9b
8.98
7.78
7.78
7,16
8.39
8.30
9.94
9.47
9.57
9.71
o39
9.10
9,46
9.41
6.65
8.97
-.47
8.o4
7..3
9.33
9.16
7.60
8.10
7.71
.58
8.81
*
*
*
* *
*
-z
*
* *
*
* *
* *
*
8.28 8.52
14.05 14.20
11.3 10.87
11.4 11.20
*
*
*
7.56 7.72
9.09 9.70
9.90 10.30
9.44
.Gf
7.22 t76
7.91
9.40 9.27
'-
*
* *
*
8.b 8.01
11,13 11,33
QJ
*
*
* * *
*
* * *
-
1L
Table 3 continued
The 2-nitro-1,3-indandiDnates of the aromatic
anies.
the 2-nitro-1,3-indandionato of
m.p.
°C.
N...
N
caic. found
soluble in
-
SLp1e:
N-ethyl aniline (4)
N-propyl aniline (4)
N-butyl anilLie (4)
8.98
8.59
8.24
8.24
18$
191
209
N-isobutl aniline (4) 207
N-methyl-o-toluldine (4)190
N-ethyl-o-toluidine (4)192
8.8
N-iiethyl-a-naDh hyi
amIne
199
N-inethyl-b-naphtthyi
amine
177
amIne (4)
8,62
8.84
8.05
7.93
*
*
*
*
*
* *
*
*
*
*
* * *
. i.
ia L.
c
. j. S
Dimethyl aniline (3)
133
o-DIiethy1 toluidine( 4)150
p-Dlcthyl toluluine (4)149
a-DIethyi naihthyl
9,0.
8.59
.59
N-ethyl-p-toluldine (4 )1ô4
8.82
8.54
8.29
1.
153
*
8.05 .32 * *
:;.59
7.9].
9.07
8.43
8.21
* * * *
* *
7.73
7.65
* * * *
8.96
*
Phenol:
o-Ainophnol
m-Aminophno1
p-Aftopheno1
,4-Liainoinol
1-amino 2-nahthl
205
210
-
200
Ether:
o-Phenotldtna
m-Phenetidine
p-Phenetidine
o-Anisidine
m-Anisiuine
p-AnisLiine
o-Dianisidine
Halo en:
o-Chloroariiline
rn-Chloroaniiine
p-Chioroaniiine
5-lono 2-toluluine
206
210
i20
18
205
203
226
182
192
188
lT2
300
300
300
315
350
*
* * *
328
328
328
314
314
314
313
*
* * *
316
* * *
*
*
*
*
*
3m
31$
424
*
* *
* *
*
*
*
*
*
12
Table 3 continued
The 2-nitro-i,3-indandionates of the aromatic
amine3.
the 2-nitro-1,3-indan- m.p.
OQ,
dionate of
N..
soluable in
N
caic. found
1
Nitro:
162
o-Ni troaniline
132
m-Nitroaniiine
175
o-Nitroaniiine
3-Iitro-4-aminoto1uene 156
Ketone:
2-Arnicoaceterohenone
4-AirLicoaeetohenone
p-Diniethyl aninobenzalaehyao
134
199
329
329
329
343
* * * *
* * *
* * * *
*
326
323
*
*
134
**
**
oil
oil
,p' -Potraethy1da'Ino-
benzonbeione
Acid aric acid de'ivatLve:
m-Aminoberizoic acid
o-Ainobenzoid acid
p-kminobenoic acid
Ethyl anthranilate
Methyl nthraniiate
p-AmIno acetinil1ie(4)
Benz&iciine (4)
Sulfa ilaniae
o-Toluidiue-5-sultorii c
acid
212
159
213
197
137
212
19c
214
-
14
164
358
34.
363
395
208
Antbrani1aicte
Azo and azine:
145d 295
3enzalazine
375
Tiycirazobenzene
Direthji a; 1noazobenene18B
Diazoa1inobenzene
191
2c;9
11.77 12.15
13.51 13.52 *
7.71 7,s4 *
*
7.09
6.59
**
7.11
.36 *
*
9.49 953
11.20 11.01 * *
13.4t 13.41
12.09 12.31
*
*
13
Table 4
The 2-nitro-1,3-indan<iinates of the heterocyclic
amines, -
the 2-nitro-1,-inda;-
dionate of
ni.p.
00
SiraiDle:
l6
Pyridine (4)
161
a-Picolino (4)
146
b-Picoline
175
g-Picoline
155
Quinoline (4)
2-Methyl quinoline (4) 157
4-Me thyl qulno1ini
6-Methyl quinolLne
7-iUethyl quinoline
8-Methyl qulnoline (4)
Acridine (4)
Isoquinoline
18
161
162
160
185
18?
2Pheny1, 4, ó-aiLaethyl142
pyriiui1ine
Piperidine (4)
yrrolicLine
iioDTho11ne
12
215
d,
Acid anu aciu dexivative:
171
Nicotinic acid
198
Nicotiniide
143
Ethyl nicotine
N
N.E.
cab, found
270
10.37
9.85
9.85
9.85
.75
8.38
8.38
6,58
8.38
8.38
7.57
284
284
334
334
334
320
575
N.$.
N. :.
/Q
1).60
soluble in
*
9.77
9,96
9,71
8,63
* *
* *
* *
* *
8. 46
* *
* *
8.3
8.39
8.17
8.11
7,60
***
*
8.94
* * * *
*
* *
* *
*
*
10.15 10.20
10.68 10.89
10.07 10.22
* * * *
* * * *
* *
0.75
157
313
*
* *
* *
16i
3
* * * *
151
444
* * * *
it2
365
365
* *
* *
oline
159
7-Methyl-S-ni tro uin136
oline
5-Methoxy-3-nitroquin179
oline
379
Creattnne (1)
Halogen:
4,7-Dic1oroquLio1ine
5-rouo--ni tro- quin-
olino
Nitro:
5-Nitroquinolin
8-NitroquinolirAe
5-Methyl-b-ni tro quin-
-
18
32
-
*
379
* * *
395
* *
14
Table 4 continued
The 2-nitro-1,3-inciandionates of the heterocyclic
axnines.
the 2-nitro-1,3-indan- m.p.
dionato of
°C.
Amine 3
2-Amino pyriciine (4)
2,6-Diaminopyridine
2-Amino- 4-me thyl-pyrim-
idine
2, 4-Dihydroxy-6-aminopyriiidine
199
235
245
177
300
-
5-Amino uracil
2-Amino thiazol
20
4(2' ,3' -Dih7aroxToroyiamine ) -6-chioro quin-
207
azoline
4(w' -hyc1roxyhery1anine )6-chloroquinazolino 168
4(2' -hydroxyethyianiine)quinazoline
243
Alkaloid:
186
Quinine (4)
Strychnin (4)
226
185
i3rucine (4)
Alypine (2)
Berberine (2)
Brucine (2)
p-Phetonine/ (2)
ucaine A (2)
Piprazine (2)
Thoo bromine (2)
Theophylline (2)
%N
cab, found
oil
3l
soluble in
-
14.67 14.60 *
*
*
318
291
*
455
****
****
40
**
389
*
8,14 7.94
8.00 7.42 *
7.19 6.92 * *
15
DISCU3SIOi OF
ULTS
2-Ni tro-1, 3-incLandione for..is crsta1iine, sharp
melting salts in acetone solution with both the simile
and substituted amines, such as the amino acids, proteins,
hydroxylanthes, amides, halo-, azo-, and nitroamthes.
Accurate neutralization equivalents may be determined
for the salts of the veak and moderately weak bases such
as aniline and quinoline but not for the weak bases as
the mono-, di-, and trialkyl amines, morpholixie, and
piperidine.
The base may be. regenented by the addition
of alkali to the salt.
The solubility of the salt: of the aliphatic primary and secondary amines decreases in the polar solvents and increases in the non-polar solvents with increasing molecular
eight.
The melting points of the
salts of the iso-amines are higher than the normal amines
The salts of the aromotic arid hoterocyciic amines are
even less soluble in the non-polar solvents than are the
aliphatic aninos.
Substitution of a nethy1,
ydroxy, or
amino group decreases both the melting point and the
solubility.
The substitution of a hal:gen, nitro, or
carboxyl groups increases the solubility.
The keto active compounds, hydrazine, pheny1hy
drazine, hydroxylamiue, sor.icarazide, give yellow salts
16
which, on slightly warming, split out 'hater to form
co1ored precipitates. Usually a iixture is formed con-
sistniz of salt, -azone, and -azone salt that is iripossible to &erarte.
The slts are either wilte or a ltrht yellow, with
the exception of the golden-brown dimethylaminoazobenzene.
17
BIBLIOGRA.PHY
rnest. tber daa 2-Nitro-indandion-(1.3) ala
Basenf&llungsmittel. Zeitsohrift ftr physiologisohe
1. M11er,
Chernie 269:31-.2, 1941.
2. Rosenthaler, L,
Basen.
2-Nitro-1.3-indandion ala Reagens aus
Soientia Pharmaceutia 9:6, 1938.
3. Wanag, Gustay.
2-Ilitro-indandion-(l.3) tnd seine Saize.
Berlohte der deutsohen Chemisohen Gese11haft 69B:10661074, 1936.
4. .Wanag, Gustav und Lode, Arnold.
Verwendung von 2-Nitro.-
indandion-(1.3) t&r die Isolierung und Identifizierung
organisoher Basen.
Beriobte der deutsohen Chemisohen
Geselishaft 70B:547549, 1937.
5. Wanag, Gustav und Lode, Arnold.
Versuohe zur Darstellung
des Ninhydrin aus 2-Nltro-indandion-(1.3).
Beriohte der
deutsohen Chemisohen Gesellshaft 71B:l267-1272, 1938.
6. Wanag, Gustav wid Lode, Arnold.
B-Oxime des Indandion-
(1.3) oder 2-Nitroso-indandion- (1.3)
Beriohte der
deutohen Ghernischen Gesellshaft 72B:49-50, 1939.