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Book Review Lexikon alchemistisch-pharmazeutischer Symbole (Dictionary of Alchemical-Pharmaceutical symbols) by W.

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The term “phostamic acids” is applied by B. Helferich and
U.Curtius to a new class of compounds of general formula I.
The term was chosen by analogy with the term sultams for
0
t
~-(CHZ)~-P--OH
L
N-.A
I
r-(CHz),--SOr
I
I
L -N-A
[(CHI),N-CHZ-CH~T]@ OHQ -+ (CH,),N
R
R
The Hofmann degradation of tritium-labelled quaternary ammonium salts has been studied by F. Weygand, H. Daniel, and
H . Simon. Decomposition of trimethyl-ethyl(2T)-ammonium
hydroxide (I), in vacuum at 4OoC or in glycol at 18OoCor
with superheated steam, gave non-radioactive trimethylamine, indicating exclusively p-elimination.
(0
I1
I
0
t
CI-(CH&-P-NHR
I
NHR
0
t
+ r-(CHz),-P-NHR
I
NaOH
--
L--NJ
Trimethyl-ethyl(2T)-ammonium iodide (11) and trimethyl(T)-ethyl-ammonium iodide (111) were subjected to the
modified Hofmann degradation with phenyl-lithium (2 moles)
in ether.
R
[(CH,)~N-CHZ--CH~T]@18, [ ( C H ~ ) ~ N - C H ~ - C H J ]1
@
8
I11
IV
compounds of structure 11. Amides of the phostamic acids
(111, n = 3 or 4) are obtained from w-halogenoalkane-l-phosphonic diamides (IV) by boiling with caustic soda in methanol.
The yields Iie between 33 and 75 X. The phostamic amides are
slightly hydrolyzed by acids even at room temperature. Attempts to obtain free phostamic acids from w-haloalkane-lphosphonic amides have not yet succeeded, evidently on account of the excessive sensitivity of the free acids to alkali. /
Liebigs Ann. Chem. 655,59 (1962) / -Hg.
[Rd 3161102 IE]
+ CHzzCHT + HOT
+ HOH
1
CHzT
(11)
(111)
Compound (11) gave trimethylamine containing ca. 80 % of
the possible tritium activity; it follows from this that the
primary reaction is the splitting-off of a proton from a
methyl group and that the degradation is accomplished by
a,@-elimination.
(11)
-GH6
+ CsHsLi +
8
(CH&N-CHz-CHzT
+ (CH3)rN
I
I
+ CHz=CHz
I
CH2T
Simultaneous oxidation and esterification of p-xylene to give
dimethyl terephthalate (I) is reported by U.Maffezzoni and
E. Alneri. A mixture of methanol and air in a ratio of 1:1 by
volume is allowed to react with p-xylene in a steel autoclave
at a temperature of about 200°C and 10-15 atm pressure.
Cobalt salts (about 1-2 g per kg reaction mixture) act as
catalysts. Under these conditions, methanol is fairly stable to
oxygen, so that the yield of I is 95 %, calculated on the xylene
or 60-70 % calculated on the methanol. Formaldehyde,
formic acid, carbon monoxide, methyl formate, and dimethoxymethane are formed as easily separable by-products.
The new process, which may be operated either continuously
or batchwise, has considerable importance in view of the
rapid development of poly(ethy1ene terephthalates), because
production can be increased and investment and operational
costs reduced in comparison to the current two-stage processes. / Chim. e 1‘Ind. 44,631 (1962) / -Pf. [Rd 314/101 IE]
(CH&N
The olefin contains relatively little tritium, indicating a
strikingly small isotope effect. The homologous trimethyl-npropyl(2T) - ammonium iodide shows the same behaviour on
treatment with phenyl-lithium, and (111) yielded unlabelled
ethylene. / Liebigs Ann. Chem. 654, 111 (1962) / -Sk.
[Rd 301/93 IEI
The reaction of dehydrobenzene with thio-ethers has been
studied by V. Frauen, H.-I. Joschek, and C . Mertz. Dehydrobenzene (obtained from o-chlorobromobenzene and
butyl-lithium) reacts with dimethyl sulphide to yield on
carboxylation S-phenyl-thioglycollic acid (X), providing excess butyl-lithium is used. With one equivalent of butyllithium, methylphenyl sulphide (75 %) and polymethylene
are formed. It seems that fhe intermediate ylide (11) is
stabilised by butyl-lithium.
Mixed metal carbonyls are described by K.K. Joshi and P. L.
Pauson. Sodium cobalt tetracarbonyl reacts with bromomanganese pentacarbonyl in tetrahydrofuran at room temperature to give cobalt manganese nonacarbonyl (I), which
forms orange-red needles, m.p. 45-46 “C.
0
Under the same conditions, sodium cobalt tetracarbonyl
interacts with cyclopentadienyliron dicarbonyl iodide to yield
cyclopentadienyliron cobalt hexacarbonyl (11) as reddish
black crystals, m.p. 52-53OC. / 2. Naturforsch. 17b, 565
(1962) / -KO.
[Rd 342/105 IE]
+ CHz=CHT
C~HS-S-CHZ-COOH
!)-pa,
\
(I)
3
e
(11)
The polymethylene is not formed from free methylene; CHz
could not be trapped in an interception reaction. With diethyl
sulphide, dehydrobenzene (111) yields ethylene and phenyl
ethyl sulphide; however, in the presence of an organometallic base the reaction of (111) with diphenyl sulphide does not
yield an ylide. Instead the organometallic base is added onto
(111). Conversely, from triphenylsulphonium bromide and
butyl-lithium dehydrobenzene and diphenyl sulphide are formed. / LiebigsAnn. Chem. 654,82 (1962) / -Sk. [Rd 300/92 IE]
BOOK REVIEWS
Lexikon alchemistisch-pharmazeutischerSymbole (Dictionary
of Alchemical-Pharmaceutical Symbols), by W . Schneider.
Verlag Chemie GmbH., Weinheim/Bergstr. 1962. 1st Ed.,
140 pp. Price D M 14.- (about $3.75).
The depths of alchemy are particularly illustrated by th’e fact
that for some years alchemical lore has been studied not only
by chemical historians, but also by psychologists.
Angew. Chem. internat. Edit.
1 Vol. 1 11962) } No. 12
It is exceptionally attractive for the historian to compare the
tenets of alchemy with modern chemical dogma founded on
tional scientific reasoning. He is concerned with the probem, which alchemical conceptions and what part of the fund
of alchemical knowledge have influenced the development of
modern natural science.
For the psychologist, alchemy is a treasure trove of symbols
that express subconscious mental events. Because of this,
t
669
some notable investigators see in alchemical lore a forerunner
of psychology.
The liberal use of symbols is a characteristic of alchemical
literature. One encounters not only symbols used as a shorthand notation for substances or simple processes such as distillation or sublimation, but also drawn or written symbolic
pictures of whole reaction schemes for chemical conversions,
uscd a s a veil to be penetrated only by the initiate.
‘The study of alchemical literature is made more difficult by
the use of these symbols in a confusing profusion and variety
of form. Wo/&mp Schtieider’s “Dictionary of AlchcmicalPharmaccutical Symbols” is a valuable guide through this
labyrinth of prodigality and ambiguity. In this reproduction
of symbols from a work that appeared in Ulmin 1755 entitled
“Mediziniscti-Chymiscli- und Alchemistisches Oraculum”,
cnlarged by a compilation of the most frequently used abbreviations and signs and by a valuable bibliography, the
modern initiate into alchemy is offered a tool wherewith to
acquaint himself with this very interesting historical cultural
material. The use of the “Lexikon” is facilitated by a comprehensive index.
G. Hirhrr and K . Mewzi, Basel (Switzerland) [NB 893/25 IE]
Gnielins Handtiuch der anorganischen Chemie (Gmelin’s
Handbook of lnorganic Chemistry). 8th Edition, new
and completely revised. Published by the Gmelin Institute
for Inorganic Chemistry and Allied Fields in the Max
Planck Society for the AdVdnCemCnt of Science. Initiated
by R . J . M q w , continued by Erich Pietsch. Verlag Chemie
GmbH., Weinheim/BergstraOe (Germany).
This is the last article in a series of reviews of the newly
published Gmelin Supplements, which began in Angew.
Chem. internat. Edit. I , 277 (1962) and was continued in Angew. Chem. internat. Edit. I , 463 and 609 (1962). It is a review
of the three volumes published in 1961.
System No. 60: Copper, Part B, fascicle 2 Copper-boron to
copper-bismuth compounds), 1961, XLI, 352 pages with
38 figures, German-English table ofcontents,English headings
a n d subheadings on the margins of tbe text. Clothbound [*I
D M XI.--. By Olga Angerti, M . Atterer, H . Balters, K.-C.
Biwhhec~k,R . Gagarin, Emm‘rr Haller, Erna Hoflmann, K .
HolzaRfeI. E/Ierr Y . Lindeiner-Schcin, P. Stiess, and K . Swcrrs.
This fascicle Copper B 2 (352 pages with 38 figures) is a
continuation of fascicle Copper B I , which was published
three years earlier (1958j and has already been reviewed in
this journal [Angew. Chem. internat. Edit. 74, 278 (1962)J.
I t covers the compounds of copper with the elcments boron,
carbon, silicon, phosphorus, arsenic, antimony, and bismuth.
’The bulk of this fascicle (more than 70 % of the text) is
covered by the compounds or copper with carbon (252 pages).
The chapter begins with a section on copper acetylides (17
pages) and proceeds, after a brief discussion of the alleged
existence of a copper carbonyl (1 page), to the copper
carbonates (16 pages) ; the basic copper(I1) carbonates
2CuC03.Cu(OH)2 (azurite) and CuCO3.Cu(OH)z (malachite) are discussed in detail. The following large chapter on
the copper salts of organic acids (185 pages) includes the salts
of aliphatic and aromatic mono-, di-, and polycnrhoxylic
acids, unsaturated carboxylic acids, hydroxy-, 0x0-, nitro-,
halo-, and cyanocarboxylic acids, picric acid, as wel! as
aliphatic and aromatic sulfinic and sulfonic acids. This
selection of organic salts is much more extensive than that in
other volumes of the Gmelin Handbook, and is justified by
the special importance of many organic copper salts. The
selections were not only based on the importance of these
compounds, but also made to emphasize relationships. Inner
complexes of copper, as opposed to cationic and anionic
copper complexes, are not discussed in this chapter. Their
dcscription is to be included in the final fascicle of Part B of
[ * ] The Gmclin volumes after this fascicle are not available in
paperbound form.
670
Copper. For the sake of coherence, the salts of acidocuprate
ions, i . e . anionic copper complexes, are discussed here, in
deviation from the Gmelin Principle of the Last Place,
according to which they would have been discussed in the
following Copper fascicle, under the heading of the respective metal. This is useful for example in the case of copper
tartrates and Fehling’s solution (23 pages), since the complex anions play the primary part and the cations have only a
secondary role in the tartratocuprate ions which appear in
the sediment of Fehling’s solution. The cyanides, cyanates,
thiocyanates, and related compounds of copper (33 pages)
conclude this chapter. While the acidocuprate ions are discussed here as in the previous case, the corresponding metal
salts will be covcred in the subsequent Copper fascicle B 3
under the respective metals, just as in the case of the anionic
copper carbonate complexes.
The sections o n the compounds .of copper with boron (7
pages), silicon (21 pages), phosphorus (29 pages), arsenic
(34 pages), antimony (6 pages), and bismuth (3 pages) take
up much less space (100 pages in total) than the coppercarbon compounds. Worth mentioning are the discussions
of Cu-B alloys and copper borates, Cu-Si alloys and copper
silicates. Cu-P alloys, copper phosphides, and copper phosphates, Cu-As alloys, copper arsenites, arsenates, antimonates, and bismuthites. The section (24 pages) on copper
arscnite (“Scheele’s Green”) and copper arsenate (pest control, plant protection, “Schweinfurt Green”) of this part of
the volume should be of special interest.
The bibliography is complete to the end of 1949 and is
selectively quoted to 1958 in special cases. If anything must
be criticized about this volume, it is the often quite unclear
typographical arrangement of the German-English index of
41 pages. For example, it requires some effort to find where
the section on copper salts of aliphatic monocarboxylic acids
ends and the section on copper salts of di- and polycarboxylic
acids begins. Captions such as these, which appear as primary
headings in the text, are reproduced in the index in the same
type face as the individual compounds and thus lack prominence. The same applies to the indexes of other Gmelin
fascicles. For example, in the index of the volume on
calcium, discussed below, secondary captions are in many
cases bolder than primary captions. Thus, for example,
the sections “The System CaO-P205” and “The System
CaO--P205-H20”
appear in their typographical arrangement as if they were subheadings of “Calcium Hypophosphate,” although in actuality they begin a new chapter o n
calcium phosphates. Better care should have been taken in
this respect to facilitaie the use of the index.
System No. 28: Calcium. Part B, fascicle 3 (conclusion of
calciumcompounds), 1961, LXII, 912 pages with 133 figures.
German-English table of contents, English headings and subheadings o n the margins of the text. Clothbound DM 565.-.
By €3. Apel, M. Atterer, Marianne Drossmar- W O , ~H; . Gedschold, Erna Hoffmann, G. Kirschstein, P . Koch, H . K. Kuglrr,
A . Kunze, H . Lehl, J . Nugler, L . Roth, L . Thaler, Ursula
Trobisch-Raussendorf, and Hildegard Wendf.
The system number Calcium is concluded with this 91 2-page
fascicle Calcium B 3, which continues fascicle Calcium B 2
(compounds up to dithionite) published four 5 ears previously
(1957). In toto, it comprises 2056 pages with 236 figures
in two parts (A: Historical. Sonrces. The Element and Its
Alloys. 488 pages, 29 figures. B: Compounds of Calcium
1568 pages, 207 figures).
This volume contains the calcium-sulfur compounds not
already taken up in fasc;cle B 2 as well as the compounds of
calcium (System No. 28) with the elements following sulfur
and having the system numbers 10 through 27 (selenium,
tellurium, boron, carbon, silicon, phosphorus, arsenic, antimony, bismuth, alkali metals including ammonium, beryllium, magnesium). The technology of all the respective calcium compounds discussed is omitted, since this has already
been covered in fascicle Calcium B 1. In view of the great
volume of the material, this review must be limited to the
discussion of a few examples.
Angew. Chem. infernat. Edit.
I
Vol. I (1962) 1 No. 12
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