Document O11mZ0r3EqGdmr7VJ0gLOGVB1
E. I. DU PONT DE NEMOURS & COMPANY
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NEWARK PLANT i PIGMENT COLOR RESEARCH REPORT
Pyrazine Yellow Pigments
Period Covered September 1967 to September 1969 (Part Time)
FILE: 223
:
DATE: 4/27/71
NJ
KN-71-13 Copy No._Jg
1. Numerical File 2. Research Office File - 223 3. Newark Library File - 223 4. M.Hunt, Pigments, Wilmington 5. W. 6.Struve/J.jackson/A.R.Hanke/Library 6. R.H.Wetzel, Newport (Circ. and File) i 7, E. F. Klenke/B .H. Perkins/Library Q. P.J.Monahan, Newark (Vital Records) 9. N.G.Fisher, Central Research Dept., Wilmington 10. Newark Library - for Central Report Index 11. Newark Library - for central Report Index 12. E. E. jaffe 13. g . R. Aldridge 14. Extra 15. Extra 15. Extra 17. Extra 18. Extra
NEWARK PLANT
PIGMENT COLOR RESEARCH REPORT
TITLE* Pyrazine Yellow Pigments
"' '
`o September 1969 (Part Time)
Date Submitted* 2/8/71
Date Released: 4/27/71
The yellow pigment (I) from the reaction of hydrazoic acid with 10,11-diaza-trans-fluoracendione in sulfuric acid, after purification, showed poor lightfastness on Florida exposure. Its polychloro-analog (II) is a strong, intense, non-bleeding yellow
pigment that is deficient in outdoor durability.
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TABLE OF CONTENTS I. Introduction II. period covered By Report III. Nomenclature IV. Summary and Conclusions V. Patent Status VI. Discussion VII. Experimental VIII. Notebook References
Page 1 \ 1 1 2 2 3 8
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--1 -- I. Introduction
This report is a summary of the research on "diisoquinolonopyrazine" and its polychloro-analog which were synthesized in the search for a "Monastral" yellow pigment. II. Period Covered fry Report
September 1967 - September 1969 {Part Time) III. Nomenclature
The pyrazine pigment discussed in this report probably has one of the following three structures ;
The complete name of each of the three isomers follows; IA - 5/6,12,13-tetrahydrodiisoquino-(4,3-b,4',3*-e)pyrazine-5,12-dione
B 5,6,l2,13-tetrahydro-diquino-(3,4-b,3'/4,-e)pyrazine-6,13-dione C - 5,6,12,13-tetrahydro-isoquino (4,3-b) quino (3', 4 * -e)pyrazine-5,13-
dione IV. Summary and Conclusions
The yellow pigment (I) from the reaction of hydrazoic acid with 10,11-diaza-trans-fiuorenaeendione in sulfuric acid (Schmidt Reaction) probably has the IA structure/ but there is insufficient evidence to rule out alternative structures IB and ic. I, after purification to remove isomeric impurities, etc., is a greenish-yellow pigment which showed poor lightfastness in thermosetting acrylic enamel (TAE-3) on Florida exposure. The polychloro-analog (II) of I is a strong, intense, non-bleeding yellow pigment that is redder in hue than I. The lightfastness of II in thermoplastic acrylic lacquer and in TAB-3 is significantly better than that of I, but II is deficient in lightfastness versus Irgazin yellow 3 RIT or Green Gold. Large particle size It is more lightfast than small particle size ii but the former is not attractive tinctorially.
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V, Patent Status
CP-ill, Pyrazine Yellow pigments, was submitted to the Patent Liaison Group at Newport for the preparation of a composition of matter case on I, and its polychloro-derivatives.
VI. Discussion
I was prepared from indanone as follows -
fluoracendione
C/t Mg f*2.0t
diindenodihydropyrazine
The dioxime of 10,11-diaza-trans-fluoracendione in polyphosphoric acid also gave I, probably by way of a Beckman Rearrangement. The chlorination of 1 in an aluminum chloride eutectic melt gave the polychloro-analog, 21, probably the heptachloro-derivative. Attempts to prepare the octachloro-derivative of I from X by chlorination were unsuccessful. The preparation of the octachlorO-derivative of I by
the following route was also studied.
v*> V*
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10,11-diaza-trans fluoraeendione (III)
octachloro-derivative of III
The chlorination of III gave a product, presumably the octachloroderivative of III, which did not yield the octachloro-derivative of I on treatment with hydrazoio acid in sulfuric acid.
The visible absorption spectra of I and II in dimethylformaride solution were determined, JThe wavelengths { K) and molecular extinction coefficients ( ) of their absorption peaks are tabulated below.
\ (mu)
I 428 24,400 410 21,500
II 462 25,700 437 22,900
VII Experimental
* Preparation of 2-Oximinoindanone (1871/39)
Into 100 g (0.76 mole) of 1-indanone in 1 liter of benzene anhydrous hydrogen chloride was introduced for 15 min. Isoamyl nitrite
(105g, 0,90 mole) was, then, added pver 110 min, while maintaining the reaction temperature at 35-40. Benzene (50 ml) was used to rinse the
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isoamyl nitrite remaining in the funnel into the reaction which was* next/ heated at 35-40 for four hours. After stirring overnight (room temperature) the product was filtered/ washed with ligroin, and air dried.
Yield.: 109 g (9094 yield) MP 189-93
Preparation of Diindenodihydropyrazine (1871/52A)
Into a 5 1 flask was charged
1260 ml
12.594 ammonium hydroxide#
102 g (0.63 mole} 2-oximinoindanone, and
620 ml
2B alcohol
The mixture was stirred/ and treated at 28-54 (during addition) with 330 g (1.9 ,mole) sodium hydrosulfite. The mixture was stirred 3 days at room temperature/ then refluxed 15 hrs., cooled to 30/ the solid filtered, washed with water and dried.
Yield: 76 g (9394 yield) MP 223-60 Preparation of 10,ll-Diaza-Trans-Fluoracendione
(1871/52B)
76 g (0.29 mole) of diindenodihydropyrazine and 1480 ml glacial ^acetic acid were stirred in a 5 1 flask. The mixture was treated with 220 g technical sodium dichromate/ and then refluxed for 14 hrs. After cooling to 30/ the solid was isolated by filtration/ washed with 2b alcohol/ and dried.
Yields 67.6g (8194 yield) MP. approx. 350dec
Preparation of X (1871/29B-F)
Into a 500 ml flask was charged
S.5g (.03 mole) lO/ll-diaza-trans-fluoracendione # and 170 ml (300 g) Cone'd sulfuric acid.
The mixture was stirred for 5 min. to obtain solution (red) and treated over 50 min. with 4.3g (0.066 mole) sodium azide while maintaining the reaction temperature at 28-50. The reaction mixture was# then/ heated at 40-50 for 2 hours/ cooled to 30/ drowned in 2700 ml ice-water# and stirred. The solid was filtered off, washed acid free/
and dried.
Yield: 8.4g
This product was purified by recrystallizing twice from concentrated sulfuric acid.
29D Yield: 5.4g (5794 yield of IA or IB or IC)
Analysis Found: C# 68.1 H# 3.01 N# 17,4
C H wn
r-
The mother liquor from the first acid crystallization was drowned in water/ stirred# and filtered to isolate a second product.
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Yield: 2.5g
5
This product was further purified by acid recrystallizing twice from concentrated sulfuric acid.
29F Yield: 1 g (1196 yield of isomeric product)
Analysis Found: C, 66.5 H/ 3.53
N, 16.5
cipH-,nN/,o '*
c* 68.8 H, 3.18
V, 17.8
On the melting point block both of these products were largely unchanged at 400C-
1 Strongest
3200-2700 cm-1 Peak
Assignment
10/11-Diaza-transfluoracendione
1871/29D
no absorption
broad absorption
1730 1660
0*0 (5-membered ring)
< C*0--NH-(6-- membered ring)
1871/29F
broad absorption
1670
<C=0-NH- (6membered ring)
NMR SPECTRA
1871/66A1 (essentially the same as 1871/29D) was insufficiently soluble in dimethylformamide, dimethylacetamide, dimethylsulfoxide and hexafluoroacetone deuterate for an nmr spectrum. Signal averaging for 50 passes thru a 01024 computer of a deuterated dimethyl sulfoxide solution of 1871/66A1 gave a spectrum having a single fairly sharp line at SV7.5 ppm. According to Dr. Harlan Foster of Central Research (Experimental Station) the structure of the main product from the hydrazoic acid reaction is more likely IA than IB or IC based on the single line at f7.5 ppm in the nmr spectrum.
Preparation of the Dioxim^ of 10.11-Diaza-trans-fluoracendione__ (1871/61)
To a 1 liter flask was charged 14.2 g (.05 mole)of 10/ 11-diaza-trans-fluoracendione 280cc pyridine. The mixture was stirred (incomplete solution) and treated with 13.7g (.2 mole) hydroxylamine hydrochloride.
The reaction mixture was refluxed 6 hrs.f cooled to 30p. The solid
was filtered off/ washed with 2b alcohol/ and then with water until the
filtrate gave a negative test on Brilliant Yellow paper and was
chloride ion free. After drying the yield was 12,2g
MP 340-50dec
This product was purified by extraction with hot dimethylformamide.
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Analysis
-6~ Founds N, 17.1
18 H10H402 (dioxime) reg. N, 17.8
C18H9H32 (monooxime) reg. N, 14.1
Rearrangement of the Dioxime of 10.ll-Diazo-trans-fluoracendione (1871/63)
To a 1 liter flask was charged 6.2 (.02 mole) dioxime and
250 g polyphosphoric acid
The reaction mixture was heated at 170-80 for 1 hr./ cooled to 150, drowned in ice-water and stirred. The solid was filtered off, washed with water# and dried.
Yields 6 g
This product was purified by recrystallizing twice from concentrated sulfuric acid
Yields 3.1 g
The infrared spectrum and X-ray diffraction pattern of this product are identical with the spectrum and pattern of 1871/29D,respectively.
Preparation of Polychiorodiisoguinolonopyrazine (1893/2A.B)
To a 1 liter resin flask was charged 192 g anhydrous AICI3 24 g sodium chloride 3 g technical sodium fluoride.
The mixture was heated to 110-120 for 6 hrs. The reaction mixture was drowned in ice-water containing 230 cc 5N Hcl, and stirred. The solid was filtered off# washed chloride ion and acid free, and
dried.
Yields 12.1 g
MP>360C
This product was purified by recrystallizing once from concentrated sulfuric acid.
Yield (from 11 g)s 9.1 g
Analysis
Calc, for C, H Cl NO
18 2 ft 4 2 C, 36.6 H, 0.3 N, 9.5 Cl/ 48.1
Found 36.6,36.8
0.6,0.6 9.8, 9.7 44.8,44.9
Calc. for
c 18r;3C17N42
38.9 0.54 10.1 44.7
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Chlorination of 10,11-Diaza-trans-fluoracendione (1893/39A) To a 1 liter resin flask was charged 268 g anhydrous aluminum chloride 50 g sodium chloride 22.5 g potassium chloride The mixture was heated to 120-140 to obtain a melt. To the melt was added
15.5 g 10Jt 11-diaza-trans-fluoracendione The temperature of the reaction mixture was raised to 150--60 and after stirring 10 min., chlorine was passed in at 143-67 for 6 hrs. The reaction mixture was drowned in ice-water containing 500 cc 5S HCl and stirred. The solid was filtered off/ washed chloride ion and acid free/ and dried.
Yields 39 g Analysis Found: Cl/ 48.8 Calc* for C^gCl^N^Oj* Cl/ 50.6 Infrared Spectra 1730 cm"1 ( C*0/ 5-membered ring)
Attempted Rearrangement of Polvchloro-10.11-diaza-trans-fluor.~ acehdione <1893/398.0
under conditions that bring about the rearrangement of tetrachloro10/11-diaza-trans-fluoracendione to the tetrachloro-derivative of I, polychloro-10,11-diaza-trans-fluoracendione does not appear to rearrange (based on the absence of a band at 1660-1670 cm""1 in the infrared spectrum of the product.) Attempted Preparation of Octachlors-derivative of III from Nitromethane and Tetrachlorophtliaiic Anhydride
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nitromethane
2--nitr0--4/ 5/6/ 7--tetrachloro-- indandione
In an attempt to prepare 2-nxtro-4,5,6,7-tetrachloroindandione from tetrachlorophthalic anhydride and nitromethane in Nf N-dimethylaniline, the actual product was tetrachlorophthalimide. The source of ammonia may he carbamic acid (H2N-CO2H) formed by a simultaneous oxidation-reduction of nitromethane by analogy to the formation of anthranilic acid from o-nitrotoluene.
VIII, Notebook References I71 1893
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