CA1121822A

CA1121822A - Derivatives of coumarin, or benzocoumarin, which are useful as pigments

Info

Publication number: CA1121822A
Application number: CA000321189A
Authority: CA
Inventors: Richard C. Bingham
Original assignee: EI Du Pont de Nemours and Co
Current assignee: EIDP Inc
Priority date: 1978-02-13
Filing date: 1979-02-09
Publication date: 1982-04-13
Also published as: FR2416925A1; JPS54117534A; FR2416925B1; CH642074A5; IT7920136A0; GB2014180B; GB2014180A; JPS6212823B2; IT1121051B; DE2905447A1

Abstract

ABSTRACT OF THE DISCLOSURE;
Organic pigments having the following structure are disclosed:

R1 - - R2 - - R3 where R1 and R3 are , , and and R2 is;

and wherein X1 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine;
X2 is hydrogen and CONHAr, wherein Ar is phenyl and phenyl substituted with alkyl of 1 to 3 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlo-rine, bromine, carbonamido, sulphonamido, and phthalimido;
X3 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine;
X4 is hydrogen, alkyl of 1 to 4 carbon atoms, chlorine and bromine;
X5 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine bromine and nitro; and Y1 and Y2 are each hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine.

Description

11~18'~Z

BACKGROUND OF THE INVENTION
This invention relates to derivatives of coumarin and benzocoumarin which are useful as pigments that are primrose yellow to orange in color.
Heavy metal yello~ pigments such as lead chromate, cadmium sulfide, and nickel titanate have been widely used in the paint and plastics industry for many years. However, the potential toxicity and environmental problems associated with their production and use has recently caused industry to search ~or alternatives to these heavy metal pi~ments.
Organic yellow pigments free from heavy metals provide a possible alternative to the inorganic yellows currently in use. Such alternatives must, however, offer excellent bleedfastness and durability. They also must offer bright intense shades so that they may be extended with a white pigment, such as TiO2, to obtain needed opaclty while retaining the needed color strength. The available or~anic yellow pigments do not satisfy all of these requirements.
There are six basic types of organic yellow pi~-ments currently in use (Reference: J. Lenoir in "The Chemistry of Synthetic Dyes", Vol. V, K. Venkataramen, Ed., Academic Press, New York, 1971). These are ~onoazo, diarylide, condensation azo, isoindolinone, anthraquinone, and metal chelate pigments. Each group suffers from one or more disadvantages. Monoazo yellows generally have poor bleedfastness and marginal durability.
Diarylide yellows have poor durabi'ity. Condensation azo yellows have marginal durability and are expensive to use. Isoindolinone and anthraquinone yellows have relatively low color strength and are expensive to use.
Metal chelate yellows are dull, often green pigments which do not completely avoid the heavy metal problem.
The present invention relates to a ne~r class of ~ellotJ to orange organic pigments. These new compounds provide bright intense colors which exhibit excellent bleedfastness and durability. They are particularly useful in the pigmentation of paints, plastics, and inks and they offer excellent alternatives to the potentially toxic in-or~anic pigments currently in use.
SUMMARY OF THE INVENTION
This invention relates to pigments which arederivatives of coumarin, 5,6-benzocoumarin and 7,8-benzo-coumarin and which have the formulas:
O
Rl CNH 2 3 where Rl and R3 are II ~

X ~ , and

2 o x4 III

and R2 is 11~18Z2 IV ~
X~ \~

and R2 is y V ~ and Y
VI

wherein Xl is hydrogen, alkyl of 1 to 4 carbon atoms,alkoxy of 1 to 4 carbon atoms, chlorine and bromine;
X2 is hydrogen and CONHAr, wherein Ar is phenyl, and phenyl substituted with alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlo-rine, bromine, carbonamido, sulphonamido, benzimidazolone and phthalimido;
X3 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine;
X4 is hydrogen, alkyl of 1 to 4 carbon atoms, chlorine and bromine;
X5 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine, bromine and nitro;
and Yl and Y2 may be the same or different and are each hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine.

11;~18:~'Z

DETAIL~D DESCRIPTION OF THE INVENTION
As stated above the present invention relates to a new class of organic pigments which vary in color from yellow to orange. These new compounds provide bright, intense colors which exhibit excellent bleedfastness and durability and are characterized ~y Formula I. The com-pounds of this invention are derived from coumarins or benzocoumarins.
It will be understood that this invention includes pigments derived from benzocoumarin which are represented by the formulas:

~ H 2 ~ ~

wherein Xl is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine;
X2 is hydrogen and CONHAr, wherein Ar is phenyl, and phenyl substituted with alkyl of l to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine, bromine, carbon-amido~, sulphonamido, benzimid-azolone and ph~halimlde; and Yl and Y2 are each hydrogen, alkyl of 1 to 4 ^arbon atoms, alkoxy of 1 to 4 carbon a~oms, clllOrine and bromire.

3o 1~18~2 VIII ( ~ o Yl ~ r x ~,=/ ~ ' fO

wherein Xl is hydrogen, alkyl o~ 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine;
X2 is hydrogen and CONHAr, wherein Ar is phenyl, and phenyl substituted with alky of 1 to 4 carbon atoms, aikoxy of 1 to 4 carbon atoms, chlorine, ~romine, carbonamido, sulpllonamido, ~enzi~llid-azolone and phthalimido: and Yl and Y2 are each hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bro~.ine.
This invention further includes pi~ments der ved ~rom benzocoumarins which are represented by the follo in~
formulas:

X '~ ' ~ 4 wherein X3 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlo~ine and bromine;
X4 is hydrogen, alkyl of 1 to 4 carbon atoms, chlorine and bromine, and Yl and Y2 are each hydrogen, alkyl of 1 to 4 11~18~'2 carbon atoms, alkoxy of 1 to 4 carbon atoms, chloro and bromo.

~ ~ " ~ N-C ~ ~
x3 H H O O x3 wherein X3 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine;
X4 is hydrogen, alkyl of 1 to 4 carbon atoms, chlorine and bromine; and Yl and Y2 are each hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine.
This invention also relates to compounds derived from coumarin which are represented by the following formulas:

XI X ~ C - N ~ N-C - ~ X5 wherein Xl is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine;
X5 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine, bromine and nitro; and Yl and Y2 are each hydrogen, alkyl of 1 to 4 car-bon atoms, alkoxy of 1 to 4 carbon atoms, chloro and bromo.

11~18,ZZ

It will be unders-lood that toe com ~ (ls ler--v-ed from coumarin and biphenyl or substituted biphenyl diamine are represented by the formula:
Xl Xl XII ~ N~J N-C~ 5 wherein Xl is hydrogen, alkvl of 1 to 4 carbon atoms al'~oxy of 1 to 4 carbon atoms, chlorine and bromine;
X5 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine, bromine or nitro;
Y1 and Y2 are each hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine.
It will be understood that those compounds of Formulas ~II to X are preferred in which Xl, X3, X4, Yl and Y2 are hydrogen, methyl and methoxy, and in which X2 is hydrogen and CONHAr wherein Ar is phenyl substituted with methyl and methoxy.
It will also be understood that those compounds of Formulas XI and XII are preferred in which Xl, X5, Y
and Y2 are hydrogen, chlorine, methyl or methoxy.
Most preferred compounds of this invention are those compounds of Formula XI in which X1, X5, Yl and Y2 are hydrogen, chlorine, methyl or methoxy.

The compounds of this invention vary in color from greenish yellow to reddish yellow shade range. For example, when Xl and X5, and Yl and Y2 of the compounds of Formula XI are hydrogen the compound is a bright medium ZZ

shade yellow, but when Xl or X2 are halogen or nitro and Yl or Y2 is alkyl or alkoxy, the compound is of a reddish hue. Therefore, by varying the various substituents on the compound's backbone, one can obtain numerous shades of yellow to orange pigment.
It should also be understood that the compounds of this invention have very low solubility in organic solvents and show excellent bleed resistance in typical alkyd or lacquer paints as determined by an overstripe bleed test. In addition the compounds of this invention also exhibit excellent resistance to migration in plastics such as polyvinyl chloride.
It has been observed that, in general, those compounds of Formulas XI and XII are more lightfast ~hen dispersed in a typical paint or plastic dispersion and exposed in a fadeometer than the compounds of Formulas VII
to X when the substituents are the same. However, it has also been observed that, in general, those compounds of Formulas VII to X are more heat stable when dispersed in a typical plastic dispersion than those compounds of Formulas XI and XII when the substituents are the same.
The compounds of this invention can be prepared by various methods. The preferred method for preparing the compounds of this invention involves heating an appropriate coumarin or benzocoumarin carbonyl chloride with an appropriate aromatic diamine ir. the presence of a suitable solvent such as _-dichlorobenzene, a mixture of toluene and triethylamine or Dowtherm~A, (a eutectic mixture consisting of 23.5 weight percent of biphenyl and 76.5 weight percent of diphenyl oxide).

11;~18~2 An alternative method for preparing the compounds of this invention involves heating a carboxylic acid ester of an appropriate coumarin or benzocoumarin with an appropriate aromatic diamine in the presence of a suitable base and suitable solvent.
Example 1 A ~ixture of 50 ~ of 5,'-benzocoumarin-3-carbon!l chloride, 10.5 g of ~-phenylened~amine, and 1000 ml of o-dichlorobenzene is heated at 14~-150C. for six hours. ~he ~roduct is isolated by f ltration of the hot mixture, ~s rashed with dimethylformamide, and is then washed with methanol. After drying, the yield i~ 50 g of M,;"-~-phenylene bis(3-oxo-3H-naphtho[2,1-b]pyran-2-carboxamide) as a yellow crystalline solid.
Anal~ calculated for C34H20N2O6; C, 73-6; H, 3-9;
N, 5.3; Found: C, 73.9i H, 3.7; N, 5.1 Example 2 A mixture of 13.4 g of ethyl-5,6-ben~ocollmarin-

3-carboxylate, 2.7 g of p-phenylenediamine, 4.9 g of ~otassium acetate and 150 ml o~ ~o~rtherm~ A (an eutectic mixturt? of 23.5% of diphenyl a~d 7~.5% of dipheny] oxit3e!
s heated at 200C. for 10 hours. The p-oduct is ~solated by filtration of the reaction mixture and ~tashed first :rith methanol, then ~ta~er, then hot di~ethylformamide.
~he yield is 9.2 g of N,N'-n-phenylene bis(3-oxo-3H-naphtho[2,1-b]pyran-2-carboxamide). Infrared ant~ ele-mental analyses confirm that this product is identical to that prepared in Example 1.

3o 8:~2 Example 3 ~ ~-x~ure OT~ 3.0 ~ ~ 5,~-Derzoccumarin-3--arbonJl chloride, 1.4 ~ of ~-chloro-r-pherylenediamine sulfate, 10 ml of triethylamine, and lnO ml of toluenP is stirred at room terperature for OnQ h~ur ar~ ther heated at 110C. ~or four hours. The product is isolated by f;l-tration of the hot mixture and washed ~irst with metha~ol, then water, and then dimethylformamide. The compound is ~urified by extraction with 15n ml of boilin~ dimethyl-~ormamide. After dryin~, the yield is l.l G of N,M'-(2-chloro-1,4-phenylene)bis(3-oxo-3H-naphtho[2,1-b]pyran-2-carboxamide) as a reddish-yellow crystalline solid.
Anal. calculated for C34HlgN2O6Cl; C, 69.6; H, 3.3;
N, 4.8; Cl, 6.0; Found: C, 69.4; H, 3.7; N, 5.0, Cl, 7.1.
Example 4 A mixture of 16.5 g of 2-methoxy-4-nitroaniline, L.Q ~ of platinum oxide, and 2no ml of o-dichloroben7ene s shaken in a hydro~enatlon bomb in the presence of a ^on tant lO0 psi hydro~en atmosphere until hydro~en up-take ceases. The hvdrogenation mixture is then heated toapproximately 100C. and filtered to remove p]atinum which is the hydrogenation catalyst. The filtrate is combined ~.~i'h 50 g of 5,6-benzocoumarin-3-carbonyl chlo-ride and 300 ml of additional o-dichlorobenzer.e ard heated at 15nC. for six hours. The ~roduct is collected by filtration. It is purified by mixin~ :r~ th 1000 ml of dimethylformamide, filter'ng, washing with metha~ol, and ~rying. The yield is 42.3 ~ of N,M'-(2-methoxy-1,4-phenylene)bis(3-oxo-3H-naphtho[2,1-b]pyran-2-carboxamide) as a reddish-yellow solid.

Anal- calculated for C34H20N26; C, 73-6; H~ 3.9;
N, 5.3; Found: C, 73.9; H, 3.7, N, 5.1.
Example 5 A mixture of 17.5 g of ~,6-b~rzocoumarin-3-^~rbon~Tl ~hlori~e, 6.o g of 2,5-dichloro-o-~hen~ n? ~,d 1000 ml of o-dichlorobenzene is heated ~t 150C. for six hours. ~he compound is isolated by filtration and ~ashed first with dimethylformamide and th~n metha~ol.
Aft~r dryin@, the ~ield is 12.8 g of N,N'-(2,5-dichloro-1,4-phenylene~bis(3-oxo-3H-naphtho-[2,1-b]pyran-2-carboxamide) as a yellow crystalline solid.
Anal. calculated for C35H22N2O7;
N, 4.5; O, 11.4; Found: C, 65.8; H, 3.3; N, 4.6; O, 11.4.
Example 6 A mixture of 25 g of 5,6-benzocoumarin-3-carbonyl chloride, 8.1 g of 2,5-dimethoxy-p-phenylene-diamine and 1000 ml of o-dichlorobenzene is heated at 150C. for six hours. The product is isolated by filtration and washed with dïmethylformamide, then with methanol. After drying, the yield is 24 g of N,N'-(2,~-dimethoxy-1,4-phenylene~bis(3-oxo-3H-naphtho[2,1-b]pyran-2-carboxamide) as an orange cyrstalline solid.
Anal. calculated for C36H24N2O8; C, 70.6; H, 4.0;
N, 4.6; Found: C, 70.8; H, 4.3; N, 4.5.
Examples 7-28 Additional compounds of this invention as listed in Table I can be prepared according to the procedure de-scribed in Example 1 by heating Reactant 1 and Reactant 2 to obtain the indicated product.
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Exam~le 2~
A mixture of 15 g of 7,8-benzo-6-chlorocoumarin-3-carhonyl chloride, 2.76 g of ~-pherylen~dia~ine and 300 ml of o-dichlorobenzene is heated at 140C. for five hours.
The product precipitates and is col~ecte~ by filtr~tion of the hot reaction mixture. The ?roduct i~ wa-~ed thoroughly ~ith methanol and dried to ~iv~ 15.l~ g (9~% of theoretical) of N,N'-p-phenylene(2-oxo-2H-6-chloro-naphtho[1,2-b~pyran 3-carboxamide) as a bright yello~.~ material.
Anal. calculated for C34Hl8N2o6cl2 H, 2.~2; N, 4.51; Cl, 11.41. Found: C, 65.78; H, 3.15;
N, 4.49; Cl, 12.00.
Exam~le 30 A mixture of 14 g of 7,8-b~nzo-6-chlorocoumarin-3-carbonyl chloride, 3.37 g of 2-methoxy-p-phenylenediamine (~repared by the hy~rogenation of 4.1 g of 2-methoxy-4-nitroaniline), and 3Q0 ml of o-dichlorobenzene is heated at 150C. for five hours. The product pre^i~itates an~ is collected by filtration of the hot reaction mixture. The product is washed thoroughly with methanol and dried to give 10.5 g (68% of theoretical) of N,N'-(2'-methoxy-1,4-~henylene~bis(2-oxo-2H-6-chloro-naphtho~1,2-b]pyran-3-carboxamide) as a bright orange material.
Anal. calculated for C35H20N207C12: C, 64-53;
H, 3.09; N, 4.30; Cl, 10.89. Found: C, 64.37; H, 3.32;
N, 4.11; Cl, 11.20.
Examples 31-42 Additional compounds of this invention as listed in Table II can be prepared according to the pro-cedure described in Example 29 by heating Reactant 1 and 8,~2 Reactant 2 as taught in Example 29 to obtain the indicated product.

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Example 43 A mixture of 10 g of a coumarin-3-carbonyl chlo-ride, 2.6 g of p-phenylenediamine and 250 ml of o-dichlorobenzene is heated at 140-150C. for six hours. The product precipitates and is collected by filtration of the hot reaction mixture. It is washed with methanol and dried.
The yield is 10.3 g (96% of theoretical) of bright yellow N,N'-p-phenylene bis(2-oxo-2H-l-benzopyran-3-carboxamide), which does not melt below 350C.
Anal. calculated or C26H16N2O6;
N, 6.2. Found: C, 69.0; H, 3.8; N, 6.4.
Exam~le 44 A mixture of 21.8 g of ethyl coumarin-3-carboxylate, 5.4 g of p-phenylenediamine and 5.3 g of sodium carbonate in 200 ml of Dowtherm~ A (an eutectic mixture of 23.5% of diphenyl and 76.5% of diphenyl oxide) is heated at 200 +
5C. for six hours. A steam jacketed condenser is used to facilitate ethanol removal from the reaction mixture. The product precipitates and is collected by filtration of the hot reaction mixture. The product is washed with methanol, water and dimethylformamide. After drying, the yield is 21.5 g (95~ of theoretical) of N,~'-p-phenylene bis(2-oxo-2H-l-benzopyran-3-carboxamide).
Similar results are obtained if, for example, potassium acetate or sodium ethoxide is used in place of sodium carbonate.
Example 45 A mixture of 12.2 g of salicylaldehyde, 16.0 g of ethyl malonate and 9.8 g of potassium acetate in 200 ml of Dowtherm~ A is heated at 175C. for six hours. A steam - 11;Z182Z

,--c~eteà cc~,denser ard a -.oderate vacuum (ap~roximatel-~0 mm of mercury) are used to facilitate wa~er and ethanol removal from the reaction mixture.
The reaction mixture is cooled to room temoera-ture and 5.4 g of p-phenylenediamine is added. The reac-tion is then reheated to 200 + 10C. for six hours. After cooling to 100C., the precipitated oroduct is collected by filtration, washed with methanol and water and dried.
The yield is 15.4 g '58.5% of the~retical) of r~,N'-p-~henylene bis(2-oxo-2H-l-benzopyran-3-carboxamide).
Exa~le 46 A mixture of 35 g of coumarin-3-carbonyl chlor~de, 12 g of 2-chloro-p-phenylenediamine and 1 liter of Dowtherm~
A is heated at 100C. for six hours under a vacuum of of approximately 60 mm of mercury. The product is collected by filtration of the hot reaction mixture. It is washed thoroughly with methanol and dried. The yield is 38.3 g of yellow N,N'-(2'-chloro-1',4'-phenylene)bis(2-oxo-2H-l-benzopyran-3-carboxamide).
Anal. calc'd. for C26H15N206Cl: C, 64.14; H, 3.11;
N, 5.75; Cl, 7.28 Found: C, 64.45; H, 3.30;
N, 5.61; Cl, 7.22 The product was dispersed in thermoplastic acrylic lacquer paint by ball milling. A portion of this paint was extended with sufficient titanium dioxide pigment to give a final toner to white ratio of 5/95. Another portion of the paint was extended with sufficient aluminum flake to give a toner to metal ratio of 90/10. The three paints were sprayed on primer coated aluminum panels. The durability ~'', of the paints was determined by placing the panels outdoors in a southern exposure. After six months, the durability of the paints was superior to those prepared in a similar manner from Irgazin~ Yellow 2G1T, a commercial yellow pig-ment similar in hue to the product of Example 46, The bleedfastness of the product of this example in the thermoplastic acrylic lac~uer paint is determined by spraying the masstone color on a primer coated aluminum panel and then spraying a white overstripe lacquer film.
The panel is baked in an oven at 150C. for 30 minutes. No migration of the yellow pigment into the white overstripe can be detected, Example 47 A mixture of 12.2 g of salicylaldehyde, 16.0 g of ethyl malonate and 5.3 g of anhydrous sodium carbonate in 250 ml of Dowtherm~ A is heated at 150C. under a moderate vacuum (,approximately 60 mm~ for four hours. The vacuum is then remo~ed and 7.1 g of 2-chloro-p-phenylenediamine slurried in 50 ml of Dowtherm~ A is added in one portion.
The reaction temperature is raised to 210C. and held for two hours. The reaction mixture is then cooled to 100C.
and filtered. The product is washed with methanol and water. After drying the yield is 19.6 g of greenish-yellow N,N'-(2'chloro-1',4'-phenylene)bis(2-oxo-2H-l-benzopyran-3-carboxamide).
The material prepared in this manner is a struc-turally isomeric form of the product described in Example 46.
Although both materials have the same chemical composition, they show different X-ray spectra.

_28-11;~11!3Z2 The material prepared by the Example may be con-verted to the more desirable form obtained in Example 46 by a variety of techniques which are standard to pigment tech-nology such as acid pasting, or solvent milling.
F~Yample 48 A mixturQ of 1~ g of 6-nitrocoumarin-3-carbon~l ch]oride, 2.1 ,G of p-nhenylenediamine and 250 ml of o-dihclorohen~ene is heated at 150 + 5C. for six hours.
The product is collected by filtration, washed with methanol ~-d dried. The yield is 7.6 g of bright yellow N,N'-p-~henylene bis(2-oxo-6-nitro-2H-l-benzopyran-3-carboxamide).
Anal. calc'd. for C26H14N401o N, 10.33 Found: C, 57.30; H, 2.81;
N, 9.98 Examples 49-76 Additional compounds of Formulas XI and XII
listed in Table III may be prepared according to the procedure described in Example 43 by heating Reactant 1 with Reactant 2 to obtain the indicated product.

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Claims

WHAT IS CLAIMED IS:

1. A compound of the formula R1 - - R2 - - R3 where R1 and R3 are , , and and R2 is and wherein X1 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine;
X2 is hydrogen and CONHAr, wherein Ar is phenyl and phenyl substituted with alkyl of 1 to 3 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlo-rine, bromine, carbonamido, sulphonamido, and phthalimido:

X3 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine;
X4 is hydrogen, alkyl of 1 to 4 carbon atoms, chlorine and bromine;
X5 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine bromine and nitro; and Y1 and Y2 are each hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine.

2. A compound of the formula wherein X1 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine;
X2 is hydrogen and CONHAr, wherein Ar is phenyl and phenyl substituted with alkyl of 1 to 3 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine, bromine, carbonamido, sulphonamido and phthalimide; and Y1 and Y2 are each hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine.

3. A compound of Claim 2 where X1 is hydrogen, methyl, methoxy, chlorine and bromine; X2 is hydrogen and CONHAr, where Ar is phenyl and phenyl substituted with alkyl of 1 to 3 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine, bromine, carbonamido, sulphonamido, and phthalimide; and Y1 and Y2 are each hydrogen, methyl, methoxy, chlorine and bromine.

4. A compound of the formula wherein X3 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine;
X4 is hydrogen, alkyl of 1 to 4 carbon atoms, chlorine and bromine; and Y1 and Y2 are each hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine.

5. A compound of Claim 4 wherein X3 is hydro-gen, methyl, chlorine and bromine; X4 is hydrogen, methyl, methoxy, chlorine and bromine; and Y1 and Y2 are each hydrogen, methyl, methoxy, chlorine and bromine.

6. A compound of the formula wherein X1 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine;
X2 is hydrogen and CONHAr, wherein Ar is phenyl and phenyl substituted with alkyl of 1 to 3 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine, bromine,carbonamide, sulphonamido and phthalimido; and Y1 and Y2 are each hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine.

7. A compound of Claim 6 wherein X1 is hydrogen, methyl, methoxy, chlorine and bromine; X3 is hydrogen and CONHAr, wherein Ar is as defined in Claim 1; and Y3 and Y4 are each hydrogen, methyl, methoxy, chlorine and bromine.

8. A compound of the formula wherein X3 is hydrogen, alkyl of l to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine;
X4 is hydrogen, alkyl of 1 to 4 carbon atoms, chlorine and bromine: and Y1 and Y2 are each hydrogen, alkyl of l to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine.

9. A compound of Claim 8 where X3 is hydrogen, methyl, methoxy, chlorine and bromine; X4 is hydrogen, methyl, chlorine and bromine; and Y1 and Y2 are each hydro-gen, methyl, methoxy, chlorine and bromine.

10. A compound of the formula:

where X1 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine or bromine;
X5 is hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine, bromine and nitro;
and R4 is and where Y1 and Y2 may be the same or different and are each hydrogen, alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, chlorine and bromine.

11. A compound of Claim 10 in which X1, X5, Y1 and Y2 are selected from the group consisting of hydrogen, chlorine, methyl and methoxy.

12. A compound of Claim 10 in which R4 is .

13. A compound of Claim 11 in which R4 is .

14. A compound of Claim 10 in which R4 is .

15. A compound of Claim 11 in which R4 is .

16. A compound of the formula:

where X1 is hydrogen or chlorine, X5 is hydrogen or chlorine, Y1 is hydrogen or chlorine, and Y2 is hydrogen.

17. The compound N,N'-(2'-chloro-1',4'-phenylene) bis(2-oxo-2H-1-benzopyran-3-carboxamide).