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Malonodithioamide from Dimethylaminomalonodinitrile and Hydrogen Sulfide.

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sampling errors is sometimes very difficult. The automation
of sampling is more difficult than the automation of the
analytical measuring process.
7. Conclusion
The elimination of signals due to temporary strong fluctuations and to periodic fluctuations in the process is another testing problem in the automatic control of plants.
It should be clear from the developments outlined
above that modern analysis has little in common with
the analytical chemistry of two or three generations
ago, which is still being taught in technical colleges.
The modern chemist must therefore bring himself up
ideal case
to date, and acquaint himself with this important
measured value
branch of knowledge, which links together chemistry,
physics, mathematics, biology, and medicine, as well as
>Classical chemical process
many branches of technology. Analysis can now claim
human supervision
to be an independent field of instruction and research.
Analytical measurement
analytical process control
Fig. 25.
Analytical data for the control or regulation of a chemical
Finally, Figure 25 shows the ideal combination of an
automated analysis for the regulation of a chemical
Analysts with a good training in inorganic and organic
chemistry, with wide knowledge and experience in
analytical methods as a whole, and with a deeper
knowledge of some special fields are required today in
research and industry. They should be familiar with
mathematics, physical measuring techniques, electronics, data processing, information theory, and logic,
t o enable them t o take part in the development of a
rapidly growing new field, i.e. the logical, exhaustive,
and correct evaluation of analytical information from
material processes, and their critical appraisal and
reduction to the essential facts: the optimization of
The author is grateful to the staff of the PhysikalischAnalytisches Laboratorium der BASF, and particularly
Dr. Giinzfer, Dr. Kaiser, and Dr. Seidl, as well as Dr.
Briigel and Dr. Witte, for stimulating discussions.
Received: June 16, 1969
[A 722 IEI
German version: Angew. Chem. 81, 723 (1969)
Translated by Express Translation Service, London
C 0M M U N I CAT10 N S
Malonodithioamide from Dimethylaminomalonodinitrile and Hydrogen Sulfide
onodithioamide ( 3 ) . Both products react with hydrogen
sulfide in the above mentioned solvents to give the compound ( 4 ) .
By H. Eilingsfeld and M. Patsch [*I
Dedicated to Professor B. Timm on the occasion of his 60th
N--C bonds in quaternary ammonium salts can be cleaved
reductively, e.g. electrolytically[I] or with sodium amalgam [*I.
We have observed that even hydrogen sulfide is able to
cleave an N-C bond, with reduction of the carbon released,
in the case of certain ammonium salts and tertiary amines.
This reaction of dimethylaminomalonodinitrile ( I ) with
hydrogen sulfide leads to the formation of malonodithioamide ( 4 ) in very good yields.
The reaction takes place particularly readily at room temperature in pyridine and in pyridine/glacial acetic acid and
ethanol/tertiary amine mixtures. Since malonodinitrile in
alcohol adds one hydrogen sulfide to only one nitrile group
with formation of cyanothioacetamide 131, while malonodithioamide is formed from dimethylaminomalonodinitrile
under the same reaction conditions, it is assumed that the
cleavage of the dimethylamino group takes place after the
HzS addition. Under certain reaction conditions (e.g. in
benzene at 0 "C)we have been able to isolate dimethylaminomalononitrilemonothioamide (2) and dimethylaminomal-
The ammonium salt (5)[41, which can be prepared by Nalkylation of ( I ) , also reacts with hydrogen sulfide to give(4).
In order to explain the course of the reaction ( 3 ) + ( 4 ) we
assume that a nucleophilic substitution by SH at the nitrogen
takes place, similar to that postulated in the alkaline hydrolysis of chloroamines [51. However, results of our previous
investigations do not rule out a free radical mechanism.
The thiohydroxylamine derivative which one would expect
to be formed along with malonothioamide in the cleavage of
(3j is not stable under the reaction conditions, as the behavior of sulfenamides shows; disulfide and amine are formed.
Angew. Chem. internat. Edit. / Vol. 8 (1969) J No. 10
In the case of compounds of similar structure such as aminomalonates and a-phenyl-a-dimethylaminoacetonitrile we
have not been able to split off the amino group with hydrogen
sulfide. Attempts have been made to cleave the N-C bond
in (3) with thiophenols or alkylthiols; however, the reactions
proved to be of a complex nature.
Preparation of malonodithioanlide ( 4 )
Hydrogen sulfide is passed into a solution of ( I ) (10.9 g) in
pyridine (40 ml) and glacial acetic acid (10 ml) over a period
of 10 hours at 20-25 OC. Compound ( 4 ) precipitates out on
cooling the solution; yield 11 g (82%), m.p. 185-195°C
(decomp.) [212 O C (decomp.) 1611.
Received: February 5, 1969
IZ 997 IEI
German version: Angew. Chem. 81, 741 (1969)
Publication delayed at authors' request
[*I Dr. H. Eilingsfeld and Dr. M. Patsch
der Badischen Anilin- & Soda-Fabrik AG
67 Ludwigshafen (Germany)
[l] L . Horner and A . Mentrup, Liebigs Ann. Chem. 646, 49
[2] H. Emde, Liebigs Ann. Chem. 391, 88 (1912).
[3] K . A. Jensen, H . R . Baccaro, and 0 . Burchardt, Acta chem.
scand. 17, 163 (1963); W . Walter and K . D . Bode, Angew. Chem.
78, 517 (1966); Angew. Chem. internat. Edit. 5, 447 (1966).
[4] 2. Arnold, Chem. and Ind. 1960, 1478.
[5] W. J . le Noble, Tetrahedron Letters 1966, 727.
161 H . Lehr, W . Guex, and H. Erlenmeyer, Helv. chim. Acta 27,
971 (1944).
By P . Tavs[*l
Dedicated t o Professor B. Timm on the occasion of his 60th
Until recently only few cyclic phosphines have become known
that contain, in addition to phosphorus, another hetero
atom not directly bonded to phosphorus 11-31. This communication reports o n the synthesis of perhydro-l,.l-oxaphosphorins [31, the phosphorus analogs of morpholine.
UV irradiation 141 of a n approximately 3 % ethereal solution
of an equimolar mixture of alkylphosphines RPH;! and divinyl ether for 20-40 h leads to the heterocyclic tertiary
phosphines ( 1 ) - ( 4 ) (work-up by distillation).
Reaction of 1 mole of PH3 with 1 mole of divinyl ether in
500 ml of pentane with addition of 0.05 mole of azoisobutyronitrile 141 in an autoclave at 78-80 "C for 12 hours yields
the unsubstituted heterocycle ( 5 ) . P-H absorption a t 2250
cm-1, molecular weight (determined by mass spectrometry)
104. In the 220-MHz N M R spectrum, the resonance signal
of the equatorial and of the axial ring protons of ( 5 ) is resolved into four multiplets: T = 6.0, 6.8 (0-CHp-) and T =
8.0, 8.5 (P-CH2-)[-iJ. The P-H signal appears at T = 6.85
(JP-H = 185 Hz, further splitting into triplets). P,y-Diphosphinodiethyl ether, b.p. 83-85 OC/O.5 torr, P-H absorption
at 2290 cm-1. is formed in 10% yield along with compound
( 5 ) . The fragment of highest mass in the precision mass
spectrum of the former compound is C4HllOP; = (M-H).
Its 220-MHz N M R spectrum shows two multiplets at T =
6.85 (0-CH;!) and T = 8.5 (P-CH3, as well as the P-H
signal at T = 7.5 (JP-H = 193 Hz, further splitting into
UV irradiation of compound ( 5 ) and a n excess of 1-octene
in ethereal solution leads to 4-octylperhydro-l,4-oxaphosphorin ( I ) in 68 % yield.
Received: February 5; revised: March 18, 1969 [Z 1000 IEI
German version: Angew. Chem. 81,142 (1969)
Publication delayed at author's request
[*I Dr. P. Tavs
Badische Anilin- & Soda-Fabrik AG
67 Ludwigshafen (Germany)
[1] For perhydro-1,3,5-dioxaphosphorinsee S . A. Buckler and
U. P. Wystrach, J. Amer. chem. SOC.80, 6454 (1958).
[2] For 1,3-azaphospholidines see K . Issleib, H. Oehme, R . Kummel, and E. Leissring, Chem. Ber. 101, 3619 (1968); K. Issleib and
H . Oehme, Tetrahedron Letters 1967, 1489.
[3] For 4-phenylperhydro-l,4-oxaphosphorin see H. Lecoq,
Bull. SOC. chim. Belgique 42, 200 (1933).
[4] For addition of P-H to olefins see Houben-Weyl-Miiller:
Methoden der Organischen Chemie. Thieme-Verlag, Stuttgart
1963, 4th Edit., Vol. XII/l, p. 25.
[5] 85% H3P04 as internal standard. I am grateful to Prof.
E. Fluck, Universitat Stuttgart, for recording and discussing the
[6] All the 1H-NMR spectra were recorded in C6Ds using TMS
as internal standard; the spectrum of (5) was measured in deuteriotoluene. I am grateful to Dr. W . Briigel and Dr. C. Witte,
Badische Anilin- & Soda-Fabrik, Ludwigshafen, for recording
and discussing the 220- and 60-MHz spectra.
171 The -0CH2 and P-CH2 multipletscoalesce when the sample
is heated to 90 "C.
Novel Pigments from Dichloromaleimides
,O -+R-PAO
By P. Dimroth and F. Reicheneder [ *I
Dedicated to Professor B. Timm on the occasion of his 60th
shift (ppm) [ 5 ]
+ 52
Their structures follow from the -CHz-O-CHzsignal in
the 60-MHz NMRspectrum [61 (T = 6.1-6.5) and the absence
of a P-H absorption in the I R spectrum (2300 cm-1). Compounds ( 1 ) - ( 4 ) react rapidly and quantitatively with methyl
bromide in ether at 0 ° C (quaternary salt of ( I ) , m.p. 97 to
98OC; that of ( 2 ) , m.p. 139-14OoC) and with sulfur in
boiling benzene (sulfide of ( I ) , m.p. 35-36 'C, recrystallized
from pentane; that of (2), m.p. 31-32OC, recrystallized
from methanol).
Angew. Chem. internat. Edit. / Vol. 8 (1969)
1 No. I0
We have prepared the novel pigment systems 1.1 '-diphenyl2,2',3,3'- tetrahydro(3,3'- bipyrrolo [2,3 -61quinoxaline)-2,2'dione ( 4 ) and 7-phenylbenzothiazino[2',3' : 3,2]pyrrolo[4,5-b]benzothiazine ( 5 ) by reaction of dichloromaleimides
with o-phenylenediamines and o-aminothiols respectively.
Both classes of compounds are intensely colored and exhibit
pigment-like character.
The reaction product (2) expected 111 to be formed by reaction of N-phenyldichloromaleimide (Z) with o-phenylenediamine, e.g. by heating the components in glycol monomethyl
ether, cyclizes with elimination of water during recrystallization (e.g. from D M F ) to give the quinoxaline derivative ( 3 )
in very good yields. When heated with bases such as alcoholic
sodium- or potassium hydroxide, amines, or magnesium
oxide, compound ( 3 ) undergoes condensation with elimination of HCl and formation of the isoindigoid dye ( 4 ) . The
same reaction takes place when the substituted compounds
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hydrogen, sulfide, malonodithioamide, dimethylaminomalonodinitrile
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