SE443985B - POLY (ORGANOPHOSPHOSPHENES) CONTAINING CHROMOPHORA GROUPS AND PROCEDURES FOR PREPARING THEREOF - Google Patents

Description

Wherein X is a chromophore group selected from azo, nitro, ketone, amine, anthraquinone, acridine, triphenylmethane, oxazine, phthalocyanine, indigoid and sulfur dyes, R is an organosubstituent and is selected from methoxy, ethoxy, propoxy, butoxy, isobutoxy, phenoxy, trifluoroethoxy, methylamino, ethylamino, propylamino, butylaminophenylamino and piperidino, n is an integer from 250 to 20,000 and m is an integer not greater than n comprising further compounds wherein the ratio X to R is from 1 = 1 to 1: 155,000.

It can be seen that in formula I the chromophore is covalently bonded to the polymeric backbone and in formula II it is electrovalently bonded. Formula II in fact represents an acid addition salt.

The formulas illustrate compounds in which the ratio of chromophoric groups to organo groups is 1: 3 or 1: 4. The ratio can be as high as lzl for the production of highly colored products. However, if the number of chromophoric groups becomes too large, it may adversely affect the desired properties of the polymer. The ratio can be as low as 1.5,000 for the production of lightly tinted products such as filters.

The organosubstituent is usually selected to impart some desirable property to the final product and to make it as economical as possible. In general, it is desirable to modify the water solubility of the product. This can be easily achieved by selecting a substituent or group of substituents with hydrophobic or hydrophilic properties. The most water-soluble polymers can be prepared by choosing a lower alkylamino substituent, such as methylamino or ethylamino. Water resistance is imparted in the final product by using a trifluoroethoxy group.

Those skilled in the art will recognize that steric factors must be considered when selecting organosubstituents. Substitution of one bulky substituent may inhibit the placement of another substituent. If the chromophore group is too large, it may not be possible to substitute a bulky organosubstituent. These factors will not give rise to any difficulties for those skilled in the art.

Electropositive organogroups that supply electrons to the nitrogen atom of the polymer will increase its basicity and help stabilize the product: The preferred electron-supplying groups are those which bind to the polymer by oxygen or nitrogen and include, for example, methoxy, ethoxy, propoxy, butoxy, isobutoxy, methylamino, ethylamino, propylamino, butylamino, phenylamino and piperidino.

It is not essential that all organ groups be identical.

Special properties can be built into the products according to the invention by preparing them so that they contain two or more organogroups, for example methoxy and methylamino, ethoxy and diethylamino, or butylamino and methylamino.

As will be apparent to those skilled in the art, both acidic and basic chromophoric compounds can be used to prepare compounds of formula I by selecting suitable reactants and reaction conditions.

Polyphosphazenes are strongly alkaline. Therefore, compounds of formula II are prepared by acid-base reactions between the polymer and an acidic chromophore compound. The latter compound may contain a hydroxyl group which has been made strongly acidic depending on the structure of the rest of the molecule or it may contain a characteristically acidic group, such as a carboxyl or sulfone group.

It is quite clear that the number of chromophoric groups that can be bound either covalently or electrovalently to the polymer substrate is enormous.

These include chromophores from all the common classifications, including dyes such as azo, nitro, ketonamine, anthraquinone, acridine, triphenylmethane, oxazine, phthalocyanine, indigoid and sulfur. A few specific dyes, mentioned by way of example only, which may be used for preparation of products of formula I includes: cellitone yellow, celliton orange, golden yellow, yellow orange I, celliton violet R, oil orange, pair red, cellitazole ST, yellow AB, brown V, celliton-true yellow, martins-yellow, auramine, sudan violet, sudan-green, chrysaniline yellow, proflavin and fuchsin.

Particular dyes useful for the preparation of ionic compounds include, for example, amidonaphthol brown, gallocyanin, chrysamine in acid form, benzo-true yellow in acid form, direct orange, true red, methanil yellow, victoria violet, biebrich scarlet, orange R and Rhodamine B.

All the special dyes mentioned above are illustrated by formula in The Chemistry of Synthetic Dyes and Pigments, HA Lubs, Reinhold, 1955. This publication lists, in the same way as The Color Index, a large number of other chromophoric compounds that can be used for production of products according to the invention. Those skilled in the art will, through consideration of the structures of the above compounds coupled with the remainder of this specification, particularly the examples, have no difficulty in producing hundreds of embodiments of the present invention. _ _ 4. ". ..,.,.,., .. I - s 7805437-6 4 The following equations illustrate the preparation of typical types of compounds within the scope of formula I according to the present invention. In the equations, the compounds I and II are known and are prepared by known reactions and X and R have the meanings given above: cl cl \\, / P / \ cl NN cl cl \ II / '2so ° I /, P \\ // p. \ - --- à- N = ï- cl \\ zl cl I cl 'fl I II XNa -NaCl A cl ä x I Cl Cl C1 CP cn ona MGNHZ' Menu B 3 2 CE 2 -Nacl -Hcl -Hcl _ ocH2cr ¿. X THMQ x I Name x III -I -N = P N fl iïn _N = ï ___ N = P_ fl "-N = P - N = P- - I ~ 'I = I ocu2cP3 ocn2cF3 Name Nnne Name Name III _ Iv' v Equation A 7805437-6 Acid addition salts, such as those just mentioned, are produced by typical acid-base reactions as illustrated by the following equations: and max I Ill 2 z "n W * _W-w wwx '| 2" z H' n W "" “" “W wwm 'I: i III. - x E wherein X is a selected chromophore group.

It appears from the above reactions that the molecular weight of the final polymers will depend on the molecular weight of the original polyphosphazene reactant. The most suitable compounds within the scope of the present invention are those in which n is from about 250 to 10,000. Although polymers in which n is considerably less than 250 can be suitably used for many purposes, it is common for n not to be conspicuously higher than 20,000.

The molecular weight range of the compounds of the invention will vary somewhat with the polymer and chromophore but is usually from about 100,000 to 4,000. The products of the invention can be prepared using standard polymer process procedures. They can, for example, be cast as films from solution, they can be extruded or they can be shaped.

For the use of these methods, it is best to avoid crosslinking during the production of the polymer because crosslinked polymers are generally too rigid to be easily processed. Sometimes, however, it is desirable to crosslink the product after it has been prepared, for example by heating, as in the case of vulcanization of rubber and other polymers. Crosslinking increases the dimensional stability of the polymer. A very suitable method of crosslinking is to prepare the polymers so that they contain a small number of ethylene-imino groups. Such molecules are easily crosslinked by heating at any time after preparation. The crosslinking is found to take place by a free radical mechanism in which adjacent polymer chains are joined by tetramethylene groups. In polymers prepared for crosslinking, the number of ethyleneimino groups per repeating unit is usually from about 0.000l to 0.2.

As stated above, the compounds of the invention are suitable for a wide variety of purposes. They can be made into fibers, films or countless types of shaped products.

A special advantage of the products is that they can be produced into food dyes which are not adsorbed through the intestinal wall and which are completely and safely excreted. This is especially important with dyes that are suspected of undergoing metabolism to toxic products when absorbed. These dyes can also be incorporated into color-coded coatings for pills and other drugs. Products of the present invention intended for use as food dyes will usually contain alkoxy or aryloxy substituents to increase the resistance to hydrolytic decomposition. The product selected will normally be of a Formula I type as many of the Formula II type products will be subject to displacement reactions with gastric acid.

Products selected for use as fibers will preferably have a glass transition temperature below 25 ° C and a chain length greater than 1,000 monomer residues. Since at least some degree of microcrystallinity is desired in fiber-forming polymers, the organo groups will all be identical to increase molecular orientation.

For use in films for optical filters, for photographic emulsions and the like, the degree of microcrystallinity should be low to reduce opalescence to a minimum. As with fibers, the chain length is usually over 1,000 monomer units.

A reaction such as reaction A in Equation A is normally carried out in a polar organic solvent under anhydrous conditions at a temperature of from -30 ° C to 175 ° C. It is preferred but not necessary to carry out the reaction under an inert atmosphere, such as nitrogen.

Typical suitable solvents include ethers containing up to 8 carbon atoms, esters containing up to 10 carbon atoms and awh-.aal-f »___. . 7805437-6 symmetrical or asymmetrical ketones containing up to 10 carbon atoms.

The reaction time is usually from 10 to 600 minutes.

The molar amount of chromophoric compounds used for if? composition will be selected on the basis of its desired ratio of organo- to chromophoric groups. In Reaction B can be carried out without isolating the intermediate of chromophore group-substituted polymer by adding the fluorine-substituted salt or other selected compound to the reaction mixture. Addition preferably takes place for a period of from 0.25 to 3 hours while maintaining the temperature at - 30oC to 150oC.

At the end of the addition period, the reaction mixture is allowed to stand at a temperature of from 25 ° C to 10 ° C for from 3 to 10 hours to complete the reaction. In general, the amount of trifluoro-substituted compound or equivalent compound used will be at least sufficient to replace the calculated number of chlorine atoms remaining on the polymer substrates based on the amounts of parent polymer and chromophore reactants. .

The final product can be recovered (and purified if desired) in any suitable manner. A number of methods are illustrated in the examples.

Reactions C, D and E are all substantially the same. It is convenient to carry out these reactions in the presence of a hydrogen chloride eliminating agent, such as pyridine or triethylamine. The reactions take place under anhydrous conditions. In the presently preferred process, reaction is carried out in a solvent which, of course, must be reaction inert.

Any of a wide variety of solvents that will dissolve the polymeric starting material can be used. These include, for example, aromatic hydrocarbon solvents such as benzene and toluene and cyclic ethers such as dioxane and tetrahydrofuran.

The time and temperature of the reaction will vary within very wide ranges depending mainly on the reactants selected.

The temperature range can range from -32 ° C to 35 ° C, or even the time from 2 to 48 hours.

A few simple observations will allow those skilled in the art to readily determine the optimum temperature and higher, the reaction time for a particular batch of reactants. 7805437-6 8 The different methods for isolating the final product are illustrated in the examples. Normally, the process will vary with the solubility properties of the product. If it is soluble in the organic solvent in which it is prepared, it can be isolated by evaporation of the solvent or precipitation with a non-solvent, after removal of the insoluble salt formed by the eliminating agent by filtration. If both polymer and amine salt are insoluble in the organic reaction medium, but soluble in water, the amine salt can be removed by dialysis using water.

Acid addition salts, as illustrated in formula II, are normally prepared in organic or aqueous solvents by mixing the selected reactants at a temperature of from -90 DEG C. to 1500 DEG C. The duration of the reaction is not critical and will vary considerably with the particular reactants. and the amounts used. Some reactions will be substantially complete in as little as 1 minute. Others will give optimal results only after a reaction period of 4 or 5 hours.

Typical useful organic solvents include aromatic and aliphatic hydrocarbons, ketones and ethers, preferably acetone, benzene or tetrahydrofuran.

The invention is further illustrated by the following examples.

Example 1 Polyphenyl-1-phenylazonaphthalene-2-oxy-triflourethoxy) phosphazenej The sodium salt of 1-phenylazo-2-hydroxynaphthalene is prepared with excess sodium hydride in tetrahydrofuran (THF) solution initially under a nitrogen atmosphere for 30 minutes. The color of the solution changes from red-orange to dark red as the salt forms.

A solution of sodium 1-phenylazonaphthalene-2-oxide (0.38 g, 0.00l4 mol) in THF (250 ml) is filtered through a glass frit in a Schlenk-type addition funnel through a positive nitrogen pressure in a reaction vessel which contains a stirred solution of poly (dichlorophosphazene) (1.57 g, 0.14 mol) in THF (1400 ml) under a dry nitrogen atmosphere. The addition takes place over 30 minutes. After 1 hour reaction, an ether solution (250 ml) of sodium trifluoroethoxide (39.8 g, 0.33 mol) is added slowly over 2 hours. The color of the reaction mixture changes from orange-red to brown and then to orange during the 36 hours of reaction at 2 ° C and precipitation in heptane. It is purified by precipitation twice from THF into distilled water and seven times from THF into heptane or benzene (yield 16.2 g, 51%).

. The polymer is recovered by removing the solvent at the corresponding methoxy, ethoxy, butoxy and phenyloxy compounds are prepared in a similar manner.

Analogous compounds to all the above-mentioned compounds are prepared by replacing the azo dye with celliton-yellow, golden-yellow and gold-orange I.

Example 2 POLY [(1-phenylazonaphthalene-2-oxymethylamino) phosphazenef A solution of sodium 1-phenylazonaphthalene-2-oxide (0.24 g, 1x10 mol) in THF (200 ml) is pressure filtered under nitrogen into a stirred solution of poly (dichlorophosphazene) (11, 2 g, 0.01 mol) in THF (700 ml). The total addition time is 35 minutes. After an additional 90 minutes of reaction time, the mixture is transferred to an addition funnel and added dropwise over 3 hours to a stirred solution of methylamine (43 ml, 0.96 mol) - in THF (500 ml) at 0 ° C. Atmospheric humidity is carefully excluded.

After an additional 42 hours of reaction, the solvent is removed under reduced pressure and the polymer is isolated by precipitation in heptane. Purification is performed by dialysis in water for 48 hours, centrifugation for 30 minutes at 10,000 rpm and multiple precipitation from aqueous 95% ethanol in THF or heptane until no free dye is detected spectroscopically in the precipitation medium. Yield 3.4 g, 30.4%. The polymer has an orange color. It forms hydroscopic, brittle films that were soluble in water, methanol or ethanol but are only slightly soluble in isopropanol.

The corresponding ethylamino, propylamino, diethylaxnino and anilino compounds are prepared in a similar manner.

A mixed organogroup polymer is prepared using an equimolar mixture of methyl and butylamines.

Analogous compounds to all of the above compounds are prepared by replacing the paint with oil-orange, para-red and martins-yellow.

Example - Poly [(p-phenylazoanilinomethylamino) phosphazene] - A solution of p-phenylazoaniline (0.34 g, 0.001 mol) and triethylamine (9.8 ml) in benzene (50 ml) is reacted with poly (dichloro). phosphazene) (II) (20 g, 0.17 mol) under a dry nitrogen atmosphere for 35 minutes.

The mixture is then added dropwise to a solution of methylamine (91.8 mL, 2.06 mol) in THF (700 mL) at 0 ° C under a nitrogen atmosphere. A color change from orange-brown to bright yellow occurs at this stage and a fine precipitate forms. After a further 48 hours of reaction, first at 0 DEG and later at 250 DEG C., the product is isolated and purified by dialysis in water for 5 days. Subsequent precipitation eight times from methanol in benzene ensures removal of any non-covalently bonded paint.

Yield 4.3 g, 23.4%. GPC analysis in methanol or aqueous 95% 6. UV-visible spectroscopy ethanol showed an En value close to 1.1 x 10 of solutions of 0.0205 g of polymer in 10 ml of aqueous 95% ethanol showed that (under assuming an average chain length of 15,000 repeating units) approximately six color molecules were bound to each polymer chain. The polymer forms yellow or green, brittle hydroscopic films which are soluble in water, methanol or ethanol but only readily soluble in isopropanol.

The corresponding ethylamino, propylamino and butylamino compounds are prepared in a similar manner.

The analogous compounds to all of the above are prepared by replacing the dye with celliton-orange, celliton-violet: R, cellitazole ST, yellow AB, sudan-violet and chrysaniline.

Example 4 Poly [Y1-phenylazo-2-naphthylamino-methylamino) phosphazene] A solution of 1-phenylazo-2-naphthylamine (0.5 g, 2 x 10 -3 mol) in glyme (250 ml) is added slowly over 45 minutes to a rapidly stirred solution of poly (dichlorophosphazene) (1.5.7 g, 0.15 mol) in THF (1.500 ml) under a dry nitrogen atmosphere. After 2 hours of reaction, the stirred solution is treated at 0 DEG C. with a large excess of methylamine added as a cooled liquid by means of a refrigerant oxygen cooler. The reaction temperature is allowed to rise to 25 ° C for 4 hours and the mixture is then dialyzed to remove hydrochloride salts. The resulting polymer is then isolated by lyophilization.

The corresponding diethylamino, propylamino and butylamino compounds are prepared in a similar manner except that the polymer is isolated as a film by solution casting.

The analogous compounds to all of the above compounds are prepared by replacing the chromophoric group with the chromophoric group derived from celliton-orange, cellitazole ST, yellow AB, brown V, auramine, sudan-violet or sudan-green.

Example 5 Polyph (1-phenylazo-4-p-oxophenylazonaphthalene-ethoxy) phosphazenel The sodium salt is prepared from 1-phenylazo-4- (p-hydroxyphenylazo) -naphthalene (0.25 g, 7.1 x 10 -4 mol) with excess of sodium hydride in a hot benzene-THF mixture. This mixture is then added to a solution of poly (dichlorophosphazene) (1.57 g, 0.14 mol) in a benzene-THF mixture (1.500 ml) and the reaction is allowed to proceed at 60 ° C for 12 hours. To this solution is added an excess of sodium ethoxide and the mixture is stirred at 250 for 24 hours. The polymer is recovered by precipitation from ethanol in water.

The corresponding compound in which one half of the ethoxy groups is replaced by methoxy groups is prepared in a similar manner using a 1: 1 mixture of sodium methoxide and sodium ethoxide.

Example 6 Polyfl- (p-nitrophenoxy) -butylamino) phosphase fi 3 mol) The sodium salt of p-nitrophenol (0.8 g, 5 x 10 5) is prepared by treating p-nitrophenol with aqueous sodium hydroxide solution, followed by careful drying. A suspension solution of this material in THF (200 ml) is added to a stirred solution of poly (dichlorophosphazene) (11, 2 g, 0.01 mol) in THF (700 ml) After stirring the mixture for 7 hours, an excess is added. of butylamine to and stirring is continued for 24 hours.The yellow polymer is recovered by precipitation in water.The analogous methylamino-, dimethylamineO- OCh O-tOIUiQÅiQQfj compounds are prepared in a similar manner.

The analogous compound to all of the above is prepared by replacing the chromophoric group with the chromophoric group derived from martins-yellow.

Example 7 Polypiperidinophosphazene with chromophore derived from 1,4-diaminoanthraquinone A solution suspension of 1,4-diaminoanthraquinone (0.24 g, 1x 10 -3 mol, sudan violet) in THF (300 ml) is added to a stirred solution of poly (dichlorophosphazene) (11, 2 g, 0.01 mol) in benzene (600 ml).

After 1 hour reaction at 500, the mixture is treated with piperidine.

The piperidine hydrochloride was filtered off and the colored polymer precipitated in ethanol and redissolved in benzene for casting as a film.

The analogue sudan-green compound is similarly prepared from the sodium salt of the chromophore.

Example 8 Polyphosphazene with chromophore derived from chrysaniline substituted with trifluoroethylamino and triethylamine groups A solution of 3-amino-9-p-aminophenylacridine (chrysaniline) (0.27 g, 1x 10-3 mol) in a 300 ml solution of a 50:50 mixture of toluene and diglyme is added to a solution of poly (dichlorophosphazene) & 13.7 9. 0.14 mol) in 2,000 mm.benzem. After mmrörmim; for 1 hour at ..Zšg'bnhznáíææEi fi anh fi xngenwmàiænxf fi vexškørtanrenxï flfi šßï fi lan fi ñzn = ar trifluoroethylamine and triethylamine and stir at 300 for 24 hours. The small molecule amine hydrochloride salts are filtered off and the solution evaporates to give yellow films.

Example 9 Poly [bis (methylamino) phosphazene] salt with Rhodamine B A solution of poly [bis (methylamino) phosphazeme] (Ig) in water (100 ml) is mixed with a solution of 0.2 g of rhodamine B in aqueous alcohol and Stir at 35 ° C for 2 hours. The blue-red polymer is solution-cast into a film. The strong bond of the dye to the polymer is determined by the inability of the dye to be removed by dialysis.

Other salts are prepared in a similar manner by replacing rhodamine B with amidonaphthol-brown, gallocyanin, chrysamine, direct orange, true red, methanil-yellow, Victoria-Violet, biebrich-scarlet or orange R.

The corresponding ethylamino, propylamino, ethoxy and butoxy compounds are prepared in a similar manner by replacing the starting methylamino polymer with the appropriately substituted compound.

Example 10 Polyfbis (phenylamino) phosphazene salt with real red A solution of polyphysis (phenylamino) phosphazene] (1 g) in THF is mixed with a THF solution containing 0.1 g of real red. The mixture is stirred at 60 ° C for 3 hours, cooled and isolated by precipitation by the addition of water.

Example 11 A solution of the product prepared in Example 8 (1 g in 100 ml of THF) is mixed with a solution of 0.2 g of rhodamine B in aqueous alcohol and stirred at 40 ° C for 3 hours. The polymer is solution cast I as a film.

Claims (7)

7805437-6 '13 Patent claims Poly (organophosphazene) suitable for use wherever the polyphosphazene is used and where it is desirable to add color, characterized in that it is selected from a group consisting of compounds corresponding to the formulas: fi- 'l 2 ll' X7 * '-' U '-> <I 2 ll W "“ W * “% I l__J U Formula I- L and \ RR __ i II i N = P - N = P - - Hx | I n' m RR Formula II wherein X is a chromophore group selected from azo, nitro, ketone amine, anthraquinone, acridine, triphenylmethane, oxazine, phthalocyanine, indigoid and sulfur dyes, R is an organosubstituent and is selected from methoxy, ethoxy, propoxy, butoxy, isobutoxy, phenoxy, trifluoroethoxy, methylamino, ethylamino, propylamino, bimylamino, phenylamino and piperidino, n is an integer from 250 to 20,000 and m is an integer not greater than n including additional compounds wherein the ratio X to R is from 1: 1 to l: l5000, Compound according to Claim 1, characterized in that X is a chromophore group selected from those derived from the azo dyes Celliton-yellow, Celliton-orange, Golden-yellow, Golden-orange I, Celliton-violet R, Oil-orange, Para -red, Cellitazole ST, Yellow AB, Brown V and Celliton-genuine yellow, chrysamine, Benzo-genuine yellow, genuine red, Methanil-yellow, Victoria-violet, Biebrich scarlet, and Orange R; and wherein R is selected from methoxy, ethoxy, propoxy, butoxy, isobutoxy, phenoxy, trifluoroethoxy, methylamino, ethylamino, propylamino, butylamino, phenylanino and piperidino. 3. A compound according to claim 1, characterized in that X is selected from the nitro dyes Martins-yellow, p-nitrophenol and amidonaphthol-brown. A compound according to claim 1, wherein X is auramine. 5. A compound according to claim 1, wherein X is selected from the anthraquinone dyes sudan-violet and sudan-F green. 6. att 7. att 8. att 9. att 10. att ll. A compound according to claim 1, wherein X is selected from the acridine dyes chrysaniline and proflavine. A compound according to claim 1, wherein X is fuchsin. A compound according to claim 1, characterized in that X is selected from amido-naphthol-brown and gallocyanine. A compound according to claim 1, characterized in that it is poly (T1-phenylazonaphthalene-2-oxy-trifluoroethoxy) phosphazene. A compound according to claim 1, characterized in that it is poly (η 5 -phenylazonaphthalene-2-oxymethylamino) phosphase 2. A compound according to claim 1, characterized in that it is poly (T-phenylazoanilino-methylamino) phosphase A compound according to claim 1, characterized by it is poly [TI-phenylazo-2-naphthylaminomethylamino] phosphazene 7. A compound according to claim 1, characterized by it is polyethyl-phenylazo-4-p-oxyphenylazonaphthalene A process for the preparation of a compound according to claim 1, characterized in that alternatively a chlorine atom of a compound of the formula N = 13-- i: | i CJ 1sos4s1 ~ ai * lS_ is substituted in which n defined as before, with a selected number; organo- and chromophore groups according to the following reactions Å 1 - xua mi¿ -Naci A 0 -uci f Å_ -1 å cl x Cl X »I l I l Q _ N = p _ N = p - - R = P - NI ï °? II | * ¿cl cl Cl Cl 2 cF3cn2ona Meunz B Meuuz C _NaCl -nci lfnci Q 3 Å ocnzcrj T Tune T ïnme x; I -N = p-- u = 1 = - -wv- n = 1> - -N = P - * - * ~ N = ”= P" “I QCUZCFB àCH2CF3 NHMe Nflfie NHMe NBMe a 111 IV VQ whereby reaction A is carried out in a polar organic solvent 'under anhydrous conditions at a temperature of -30 ° C to 175 ° C and r Reaction B can be carried out without isolating the intermediate of chlorophore-substituted polymer by adding the fluorine-substituted salt or other selected compound for 0.25-3 hours at a temperature of -30 ° C to 10 ° C and at the end of additive? during this period, the reaction mixture is allowed to stand at 25 ° C - 150 ° C for 3 - 10 hours to complete the reaction, and wherein reactions C, D and E are all substantially equal and y Jg-'q en .. m, .w. 7805431-6% É 16 takes place under anhydrous conditions and conveniently in the presence of a hydrogen chloride elimination agent1, or alternatively replaces all said chlorine atoms with organo groups and reacts the resulting compound with a chromophoric acid. The Firestone Tire and Rubber Co.