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Novel Pigments from Dichloromaleimides.

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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
75 1
( I ) and (2) are used as reactants. The derivatives of ( 4 ) (R1 =
R2 = H, red-violet; Rl = CI, R2= H, Bordeaux; R1= OCH3,
R2 = H, violet) thus obtained have a pigment-like character
(insolubility. thermostability, weather resistance, coloring
power); they are suitable, e.g. for the coloring of lacquers,
PVC, polystyrene, polyamides. and polyolefins.
1 3-Di(tert-butyl)-2,4-dichlorodiazadiphosphetidine
By 0. J . Scherer and P. Klusmnnn [*I
The existence of four-membered phosphorus(i1r)-nitrogen
ring compounds of the general composition (RNPC1)z (compounds in which R = C6H5 [I] and CH3 [21 have, for example,
been described) has been disputed on the basis of results of
recent investigations 13.41.
We have now been able to prepare 1,3-di(tert-butyl)-2,4-dichlorodiazadiphosphetidine ( I ) by two different methods:
(i) by reaction of lithium tert-butyltrimethylsilylamide with
phosphorus trichloride
(ii) from N-tert-butylaminodichlorophosphine(2a) by elimination of HCl (yield 60 %)
Compound ( I ) . colorless crystals having m. p. 4 2 4 4 "C
(b. p. 9&93 "C/O.l torr), is readily soluble in ether, benzene,
and CC14. A 1:2 :1 triplet (J31PNCCH = 1.O Hz) ascribable
to the (CH&C group can be observed in the IH-NMR
spectrum (60 MHz). The alternative compound, (CH&CN(PC12)2, was excluded by elemental anaIysis (e. g. C1 caIc.:
25.8%; exp.:25.1%).
Suitable for
styrene, hard PVC,
printing inks
styrene. hard PVC,
printing inks
lacquers, PVC,
lacquers, PVC,
If N-phenyldichloromaleimide is allowed to react with omercaptoaniline instead of o-phenylenediamine (e.g. by
boiling under reflux for 6 hours in glacial acetic acid - recrystallization from N-methylpyrrolidone) the polycyclic
compound (5a), a brilliant, intensely orange colored compound, is formed. The reaction can be carried out with any
substituted dichloromaleimide and o-aminoarenethiols
and thus affords a method for the preparation of a new class
of yellow to red pigments. Red pigments in particular are
obtained by anellation of the mercaptoaniline - sometimes
by using 2-amino-1-thionaphthol - or by using derivatives of N-aminodichloromaleimide (e.g. N-benzoylaminodichloromaleimide). Yellow pigments are formed when
imides having electron donors in the alkyl group (e.g. chlorine, N-chloroamide) are used in the reaction.
Received: February 5, 1969;
revised: June 18, 1969
German version: Angew. Chem. 81,742 (1969)
Publication delayed at authors' request
Dr. P. Dimroth and Dr. F. Reicheneder
Badische Anilin- & Soda-Fabrik AG
67 Ludwigshafen (Germany)
[l] L. Anschutr and Beavis, Liebigs Ann. Chem. 295, 36 (1897).
Attempts to carry out substitution reactions on ( I ) with dimethylamine or methyllithium led only to complicated
mixtures of substances.
N-AlkylaminodihaIogenophosphines RNHPXz [fim and Nalkylaminohalogenoalkylphosphines RNHPRX 171. compounds of type (2),have been little investigated; the majority
of these compounds are not particularly stable at room
temperature. If tert-butylamine is added dropwise with
cooling to PC13 or RPC12 (both components being diluted
with ether), thermally stable N-tert-butylaminochlorophosphines (2) are formed in various yields; these products
can be purified by distillation and are readily soluble in
benzene and ether.
(2a): R = CI; yield 30% (ca. 20% of ( I ) is simultaneously
formed); b.p. 53-58 "C/6 torr, m.p. -40 to -38 "C; J31PNCCH =
2.2 Hz.
(26): R = CH3; yield 40°/,; b.p. 48-52 "CIS torr, P P N C C H =
1.3, J31PCH = 11.0 Hz.
(2c): R = (CH&C; yield 80%; b.p. 35-36"C/0.1 torr; J31PNCCH = 1.0. J3IPCCH = 13.3 Hz.
Unlike compound (2a), compounds (2b) and (2c) do not
form diazadiphosphetidine derivatives on addition of bases.
Preparation of ( I ) :
A solution of (CH3)3C[(CH3)3Si]NLi (73 mmoles) Lprepared
(10.6 g, 73 mmoles) and
from (CH&CNHSi(CH&
n-C4HgLi/hexane solution (33.0 ml, 73 mmo1es)l in ether
(50 ml) is added slowly and dropwise with stirring at room
temperature to a solution of PC13 (10.0 g. 73 mmoles) in
ether (100 ml). After the exothermic reaction the mixture is
filtered through a G 3 frit, the filtrate is concentrated under
vacuum (water pump), and the residue is heated to 130 "C in
order to complete the elimination of (CH3)3SiCl. Fractional
Angew. Chem. internat. Edit. / Vol. 8 (1969)1 No. 10
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