1,4-methano-hexahalo-octahydronaphthalene-5,8-dione alkylthio ethers
United States Patent Little et al. Apr. 1, 1975 l,4-METHANO-HEXAHALO- [58] Field of Search 260/586 R, 587  
  OCTAHYDRONAPl-lTHALENE-5,8-DIONE ALKYLTHIO ETl-lERS [56] References Cited [75] inventors: Julian R. Little, Wayne; Walter UNITED STATES PATENTS Nudenberg, West Caldwell; Yong S. 2,584,139 2/1952 Lidov et al... 260/586 R Rim, Paterson, all of N I 2,886,577 5/l959 Fan 260/586 R X 2,936,262 5/1960 Gilbert..... 260/586 R X Asslgneer Uniroyal. n New York, NY- 3,225,070 12/1965 Fan 260/586 R x 3,272,872 9/1966 Raden 260/586 R X Had 1973 3,277,054 10/1966 Dissen 260/586 R x [2]] Appl. No.: 329,177  
  Primary E.\-aminerLeon Zitver Relmed Application Data Assistant ExaminerNorman P. Morgenstern [62] of Atlorney, Agent, or Firml-lubbell, Cohen &amp; Stiefel [52} US. Cl. 260/586 G. 106/15 FP, 252/8.l, [57] ABSTRACT 260/45.7 R, 260/45.7 PS, 260/2.S5. 260/45.7 P, 260/45.7 S, 26()/45.8 A, 260/45.85, 26()/45.95, 260/348 C. 260/455 A, 260/464, 260/465 G, 260/465 F, 260/465 D, 260/468 G, 260/469, 260/473 F, 260/482 B, 260/482 C. 260/484 R, 260/487, 260/488 B, 260/488 CD, 260/5l4 G. 260/566 A, 260/586 C, 260/598, 260/599, 260/607 A, 260/609 R, 260/6l1 F. 260/937, 260/611 A, 260/966, 260/DIG. 24  
 Int. Cl. C07c 49/44 A fire retardant system comprising a compound having within its structure the 1,2,3,4,9,9-hexahalo-l,4- dihydro-l ,4-methanonaphthalene-5,8-dione or 1,2,3,- 4,9,9-hexahal0- l ,4-dihydrol ,4-methanonaphthalene- 5,8-dioxy nucleus or a compound which is capable of being converted to the l,2,3,4,9,9-hexahalo-l ,4- dihydro-l ,4-methanonaphthalene-5,8-dione nucleus and requires no metal oxide addition to exert its function.  
 2 Claims, No Drawings 1 l,4-METHANO-HEXAHALO-OCTAHYDRONAPH- THALENE-5,8-DIONE ALKYLTHIO ETHERS This is a division of application Ser. No. 80,747, filed Oct. I4, 1970.  
 BACKGROUND OF THE INVENTION l. Field of the Invention This invention pertains to the field of flame retardants for polymers. More particularly, this invention pertains to improved fire retardant systems for plastics, elastomers, and articles therefrom, e.g., fibers, films, shape articles, and the like.  
 2. Description of the Prior Art The increased use of polymeric materials, particularly in the building industry, has resulted in greatly increased interest in the fire retardancy of these materials. However, at the present time most commercially available plastics do not possess satisfactory fire retardancy and this inadequacy represents one of the major obstacles to the opening of new markets and uses for these materials.  
  Presently, the most widely used fire retardant chemicals are antimony trioxide and organohalogen compounds, the best known being chlorendic anhydride (1- ,4,5,6,7,7-hexachlorobicyclo-[2,2,l ]hept-5-ene-2,3- dicarboxylic anhydride); tetrabromoor tetrachlorophthalic acid, 1,4 &#39;-isopropylidenebia (2,6- dichlorophenol) [tetrachlorobisphenol A] or the corresponding bromine-containing compound; chloran, i.e., 2,3-dicarboxyl-5,8-endomethylene-5,6,7,8,9,9- hexachloro-l ,2,3 ,4,4a,5,8 ,Sa-octahydronaphthalene anhydride; chlorinated paraffins; and dechlorane (dihexachlorocyclopentadiene).  
  The foregoing halogen compounds have only limited utility in polymer compositions due to a number of disadvantages. For example, when such halogen compounds are incorporated into a polymer, various physical properties of the polymer are modified, e.g., change in melt viscosity which requires higher processing temperatures, decrease in light stability, decrease in thermal stability, increase in density, adverse effects on heat distortion point, etc.  
  Some of these disadvantages have been overcome by the use of halogen-containing polymers as the flame retardant additive. Typical of such polymers are 2- chlorobutadiene, polyvinylchloride, chlorinated polyethylene and chlorosulfonated polyethylene. There are also, however, serious disadvantages associated with the use of such polymers. Among these are: (1) large amounts of halogen-containing polymers are required in order to obtain satisfactory fire retardancy due to the relatively low halogen content thereof; (2) the halogencontaining polymers have low thermal stabilities; and (3) the blending of the halogen-containing polymer with the polymer to be rendered flame retardant usually requires expensive processing techniques.  
 SUMMARY OF THE INVENTION We have discovered a new system of chemical fire retardants for polymeric materials, which system comprises a chemical compound having the l,2,3,4,9,9- hexahalol ,4-dihydrol ,4-methanonaphthalene-5,8- dione or 1,2,3 ,4,9,9-hexahalol ,4-dihydro-l ,4- methanonaphthalene-S,8-dixy nucleus or a compound which is capable of being converted to the l,2,3,4,9,9- hexahalol ,4-dihydro-l ,4-methanonaphthalene-5,8- dione nucleus and requires no metal oxide addition to exert its function. Preferably, the compound having the foregoing nucleus or being convertible thereto has a molecular weight not in excess of about 2000.  
  The polymeric materials are rendered fire retardant by incorporation of the fire retardant system of the present invention into the polymer.  
  The fire retardant system of the present invention may readily be incorporated into the polymeric material by a variety of methods depending on the nature of the polymeric material. Thus, for example, for those polymers which are adaptable to milling procedures and the like, the fire retardant system may. simply be physically blended with the preformed polymer. With other types of polymers which require compounding, e.g., an uncured elastomer, or cannot readily be physically blended with other materials after formation of the polymer, the fire retardant system may be added to the compounding mixture of polymerization mixture.  
  More particularly, we have found that a polymer may be made effectively flame retardant by blending into the polymer either (1) a fire retardant compound having a nucleus that is of the formula XX xx wherein X is halogen, (2) a precursor of said fire retardant compound, which precursor, upon combustion of 5 said blend, converts to a compound containing nucleus I or II, or (3) a fire retardant compound having a nucleus that is of the formula wherein X is halogen.  
  Preferred precursors contain a nucleus selected from the group consisting of x OX and wherein X is halogen.  
 Most preferred fire retardant compounds are those selected from the group consisting of and wherein X is halogen, wherein R and R can be the same or different and each may be hydrogen, lower alkyl, halogen substituted lower alkyl, halogen, nitrile, an aromatic nucleus of the phenyl series, SO R wherein R is lower alkyl, an aromatic nucleus of the phenyl series, or halogen substituted lower alkyl,  
 wherein R is hydrogen, hydroxy, alkoxy, or lower akyl, or halogen substituted lower alkyl, and wherein R and R taken together is and wherein R and R are the same or different and each may be hydrogen,  
 lower alkyl,  
 halogen substituted lower alkyl,  
 lower alkanol,  
 (CH COOH wherein n is an integer from I to 5. -CH CH=Cl-l-R wherein R is hydrogen, lower alkyl, or halogen substituted lower alkyl, -SO -R wherein R is lower alkyl, an aromatic nucleus of the phenyl series, or halogen substituted lower alkyl,  
  S [R9 i JN wherein R and R are each lower alkyl, or halogen substituted lower alkyl,  
  ll/ P wherein R and R are each lower alkoxy,  
 OCH1  
  o i /--Rl3 wherein R is lower alkyl, halogen substituted lower alkyl, lower alkoxy, an aromatic nucleus of the phenyl series, or NHR, wherein R is lower alkyl.  
  We have further discovered that when our fire retardant system is incorporated in a polymeric composition containing any of the various previously known fire retardant materials, described hereinabove, the fire retardancy is markedly enhanced to an unexpected degree.  
  The fire retardant system of the present invention may be used with a wide spectrum of polymeric compo sitions such as, for example, hydrocarbon chain polymers, natural and synthetic rubbers, resinous or rubbery interpolymers, acrylonitrilebutadiene-styrene polymers, styrene-acrylonitrile resins, foamed and unfoamed polyurethanes, polysulfones, polysulfides, epoxy resins, polyether polyepoxides, thermoplastic and thermosetting polyesters, polycarbonates, cellulose esters, urea-formaldehyde and phenol-formaldehyde resins, polyamides, etc., as well as mixtures of the foregoing with one another.  
 DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention resides in the discovery that polymeric materials may be rendered flame retardant by incorporating therein a fire retardant chemical structural system comprising a compound having within its structure the l,2,3,4,9,9-hexahalo-l,4- dihydro-l ,4-methanonaphthalene-5 ,8-dione or 1,2,3 ,4- ,9,9-hexahalo-l ,4-dihydro-1,4-methanonaphthalene- 5,8-dioxy nucleus or a compound which is capable of being converted to the l,2,3,4,9,9-hexahalo-l,4- dihydro-l ,4-methanonaphthalene-5,8-dione nucleus and requires no metal oxide addition to exert its function.  
  Certain of the materials which may be employed as our fire retardant system are novel compounds per se. Such novel compounds include those compounds defined by the following five structural formulas (formulas V-lX respectively). In these formulas X&#34; always designates halogen:  
 wherein R and R are hydrogen or taken together form the group Z is oxygen when R and R form the group IVA, and Z is =NOH when R and R are hydrogen;  
 wherein Y is oxygen or =NOH; when Y is oxygen, then R and R may be hydrogen, tertiary butyl with at least one of R and R being tertiary butyl, or R and R taken together form the group IVA; when Y is =NOH, then R and R are hydrogen;  
  f&#34; x X o R20 (VII) SO R wherein R is lower alkyl, halogen substituted lower alkyl or an aromatic nucleus of the phenyl series,  
 Rea  
 wherein R and R are each lower alkyl, or halogen substituted lower alkyl,  
 wherein R and R are each lower alkoxy,  
 wherein R is lower alkyl, halogen substituted lower alkyl, lower alkoxy, an aromatic nucleus of the phenyl series, or NHR wherein R is lower alkyl,  
 R and R can be the same or different and each may be hydrogen, lower alkyl, halogen substituted lower alkyl, -SO -R wherein R is as defined hereinabove,  
 wherein R is as defined hereinabove, with the proviso that when both R and R are then R and R may also be halogen, and further provided that when R and R are both hydrogen than at least one of R and R is a group other than hydrogen or lower alkyl having I to 4 carbon atoms, or R and R 2 taken together form the group IVA;  
 wherein R and R may be the same or different and may be hydrogen lower alkyl, halogen substituted lower alkyl, SO -R wherein R is as defined hereinabove, --SR wherein R is hydrogen, lower alkyl, or halogen substituted lower alkyl, R and R taken together may be -O;  
 (VIII) wherein R u and R may be various saturated or unsaturated aliphatic compounds, an aromatic nucleus or functional groups and X is halogen. This compound may then be subjected to various reactions well known in the art for changing the degree of saturation or functional group.  
  Suitable polymers in which the fire retardant systems of the present invention can be used include:  
  1. Hydrocarbon chain polymers, such as, for example, polyethylene; cross-linked polyethylene; polypropylene; ethylene-propylene copolymers; polymers of monoethyleneically unsaturated monomers such as styrene, alpha methylstyrene, acylonitrile, isobutylene, vinyl pyridine, acrylic acid, acrylates, vinyl acetate; vinyl alcohol; vinylethers and copolymers thereof, e.g., ethylene-vinylacetate copolymer, etc. Also included are natural and synthetic, rubbers, e.g., diene polymers such as polyisoprene (natural or synthetic), or polybutadiene (solution or emulsion prepared); copolymers or dienes with copolymerizable monoethyleneically unsaturated monomers such as styrene, alpha methylstyrene, acrylonitrile, isobutylene, vinyl pyridine, acrylic acid, acrylates, ethylene, propylene, etc. such as butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, and isobutylene-isoprene copolymer. Also suitable are halogen containing hydrocarbon chain polymers with or without plasticizers, such as polyvinylchloride, post chlorinated polyvinylchloride, chlorinated polybutadiene and the like. Suitable hydrocarbon chain polymers are described in U.S. Pat. No. 3,424,821, particularly column 2 thereof, incorporated herein by reference.  
  2. Also suitable are resinous or rubbery interpolymers having a minor amount of unsaturation, such as rubbery terpolymers of two or more different alpha olefins (usually ethylene and propylene although other pairs of monoolefins may be employed) with a small amount of at least one copolymerizable multiolefin. Usually the multiolefin contains from five to 22 carbon atoms and has two double bonds separated by more than two carbon atoms. The multiolefin ordinarily comprises from about 0.5 to not greater than about 20 mole percent of the interpolymer, and the ethylene and propylene units are present in ratios from about 1:4 to about 3:1. Examples of suitable multiolefins are straight or branched chain diolefins, such as those in which both double bonds are terminal as in 1,4- pentadiene, 1,5-hexadiene(biallyl), 2-methyl-1,5- hexadiene, 3 ,3-dimethyl-l ,5-hexadiene, 1,7-ocatdiene 1,9-decadiene, 1,19-eicosadiene, and the like; diolefins in which only one double bond is terminal such as 1,4- hexadiene, 1,9-octadecadiene, 6-methyll ,5- heptadiene, 7-methyll ,6-octadiene, l l-ethyl-l ,l 1- tridecadiene, and similar compounds in which the internal double bond is shielded. Also suitable are the bridged-ring hydrocarbons of similar nature including endocyclic hydrocarbons containing seven to 10 carbon atoms and two double bonds especially those containing a methylene or an ethylene bridge, for example: (a) unsaturated derivatives of bicyclo,[2.2.l] heptane containing at least two double bonds, including bicylco [2.2.1] hepta-2,5-diene; dicyclopentadiene (also named 2a, 4,7,7a-tetrahydro-4,7-methanoindene), tricyclopentadiene, and tetracyclopentadiene; (b) unsaturated derivatives of bicyclo-[2.2.2] octane containing at least two double bonds, including bicyclo[2.2.2] octa-2,5-diene; (c) unsaturated derivatives of bicyclo [3.2.1] octane containing at least two double bonds; (d) unsaturated derivatives of bicyclo [3.3.1l-nonane containing at least two double bonds; (e) unsaturated derivatives of bicyclo-[3.2.2]-nonane containing at least two double bonds, and the like. Preferred are dicyclopentadiene, 1,4-hexadiene, methylene norbornene and ethylidene norbornene.  
  Suitable resinous and rubbery interpolymers are described in U.S. Pat. No. 3,361,691, particularly column 1, line 37-column 2, line 3 thereof, and U.S. Pat. Nos. 3,000,866, 3,000,867, 3,063,973, 3,462,399, and 3,489,801, particularly column 1, line 67-column 2, line 35, all of said patents being incorporated by reference herein. 3. Similarly suitable are gum plastics represented by that class of materials combining plastics and rubbers. These materials, also referred to as resin-.  
 rubber blends generally comprise a mixture of a hard, relatively brittle polymer (resin) and a minor portion of a relatively soft, rubbery polymer. Particularly well known among this group of polymers are the ABS (acrylonitrile-butadiene-styrene) polymers.  
  Suitable gum plastics which can be used with the present invention are described in U.S. Pat. No. 3,489,821, particularly column 1, line 52-column 4, line 34 thereof, U.S. Pat. No. 3,489,822, particularly column 1, line 5l-column 4, line 45 thereof, said patents being incorporated by reference herein.  
  The ABS resins which best characterize the gum plastics, are made in a well known manner by interpolymerizing styrene and acrylonitrile monomers in the presence of a rubber which is either polybutadiene or a copolymer of butadiene and styrene, said copolymer containing not more than 10% by weight of combined styrene based on the sum of the weights of butadiene and styrene. Polymerization systems such as emulsion, mass, or solution are also applicable for ABS preparation. The manufacture of such ABS resins is shown in detail in U.S. Pat. Nos. 2,870,773, 2,802,809, 3,238,275, and 3,260,772, particularly column 3, lines 32-50 thereof, each of said patents being incorporated by reference herein. The ABS graft polymer-containing resins used in our invention can be made with varying rubber content, this conveniently being achieved in accordance with known practice (e.g., as shown in U.S. Pat. No. 2,820,773) by admixing additional acrylonitrile-styrene copolymer latex of grafted material, and co-precipitating.  
  It is further possible to substitute for the acrylontrilestyrene resinous portion, mixtures of styreneacrylonitrile resin and a vinyl resin such as vinyl chloride polymer (particularly polyvinyl chloride).  
  ln place of using acrylonitrile itself for the preparation of the polymer, one may substitute for some or all of the acrylonitrile, equivalent similar monomers such as homologs or substitution products of acrylonitrile e.g., methacrylonitrile, ethacrylonitrile, methyl acrylate, and the like.  
  Similarly, in place of using styrene itself in the preparation of the polymers used in the invention, one may substitute, for some or all of the styrene, equivalent monomers including substitution products of styrene, such as alkyl-substituted styrenes, including alpha-alkyl styrenes and nuclear alkyl-substituted styrenes such as .alpha-methyl-styrene, other nuclear methyl-substituted styrenes, nuclear monoethyl-substituted styrenes, the monoand di-chloro styrenes, etc.  
  4. Further suitable are foamed and unfoamed rigid polyurethanes, i.e., organic diisocyanate-modified polyesters, polyethers, polyester-polyethers and polyester-polyamides, both saturated and olefinically unsaturated. Such polymers are generally obtained from the reaction of a polyisocyanate, usually a diisocyanate, with a polyfunctional compound containing activehydrogen groups, such as hydroxy-terminated polyesters, castor oil, polyester amides and polyalkylene ether glycols as well as mixtures of two or more of these classes of polyfunctional compounds. The material used for reaction with the polyisocyanate to make the polyurethane is frequently a polyether or polyester glycol having a molecular weight of from 400 to 6,000, perferably in the l,0002,000 range. Mention may be made of chain extended polyesters made from a glycol (e.g. ethylene and/or propylene glycol) and a saturated dicarboxylic acid (e.g., adipic acid). Usually the starting glycol contains from two to 20 carbon atoms and the acid contains from four to 12 carbons atoms. Polyethylene adipate, polyethylene adipate-phthalate, polyneopentyl sebacate, etc. may be mentioned. Small amounts of trialchols such as trimethylolpropane or trimethylolethane may be included. There may also be mentioned the polyethers, such as polypropylene glycol, polypropylene-ethylene glycol and polytetramethylene glycol. Among the suitable polyisocyanates may be mentioned m-and p-phenylene diisocyanates; toluene diisocya&#39; nate; p,p&#39;-diphenylmethane diisocyanate; 3,3- dimethyl (or dimethoxy)-4,4-biphenyl diisocaynate; l,5-naphthylene diisocyanate; p,p&#39;,ptriphenylmethane triisocyanate; p-phenylene diisothiocyanate, etc. The isocyanate is, of course, used in an amount at least equivalent to the hydroxyl groups in the starting polymer; larger quantities of diisocyanate favor formation of liquid prepolymer. Generlaly the molar ratio of diisocyanate to glycol is in the 12:1 to 3:1 range. For additional examples of suitable starting materials for making polyurethanes, reference may be had to the following: Otto Bayer in Angewandte Chemie, A/59 (1947), No. 9, p. 264; and U.S. Pat. No. 3,105,062 incorporated herein by reference. Suitable polyurethanes are described in U.S. Pat. No. 3,412,071, particularly column 5, line 44-column 4, line 6 thereof U.S. Pat. Nos. 2,734,045 and 3,457,326,  
 each of said patents being incorporated by reference herein.  
  5. Also suitable are polysulfones. Such polysulfones have a basic structure of recurring units having the formula wherein E is the residuum of a dihydric phenol and E is the residuum of the benzenoid compound having an inert electron withdrawing group in at least one of the positions ortho and para to the valence bonds, where both of said residua are valently bonded to the ether oxygens through aromatic carbon atoms and wherein at least one of E or E is dinculear and at least one of the pair of nuclei are joined by a sulfone (SO group.  
  The residuum E of the dihydric phenol can be, for instance, a monomuclear phenylene group as results from hydro-quinone and resorcinol, or it may be a dior polynuclear residuum. The residuum E can also be substituted with other inert nculear substituents such as halogen, alkyl, alkoxy and like inert substituents.  
  It is preferred that the dihydric phenol be a weakly acidic dinuclear pheno, such as, for example, the dihydroxy diphenyl alkanes or the nuclear halogenated derivatives thereof, which are commonly known as &#34;bisphenols,such as, for example, the 2,2-bis-(4-hydroxyphenyl)propane, l,1bis-(4-hydroxyphenyl)-2- phenylethane, bis-(4-hydroxyphenyl)methane, or the chlorinated derivatives containing one or two chlorines on each aromatic ring. Other suitable dinuclear dihydric phenols are the bisphenols of a symmetrical or unsymmetrical joining group as, for example, ether oxygen (O-), carbonyl (-C0), sulfide (S), sulfone (SO or hydrocarbon residue in which the two phenolic nuclei are joined to the same or different carbon atoms of the residue such as, for example, the bisphenol of acetophenone, the bisphenol of benzophenone, the bisphenol of vinyl cyclohexene, the bisphenol of a-pinene, and the like bisphenols where the hydroxyphenyl groups are bound to the same or different carbon atoms of an organic linking group.  
  Such dinuclear phenols can be characterized as having the structure:  
 wherein Ar is an aromatic group and preferably is a phenylene group, Y and Y, can be the same or different inert substituent groups as alkyl groups having from one to four carbon atoms, halogen atoms, i.e., fluorine,  
 chlorine, bromine, or iodine, or alkoxy radicals havingfrom one to four carbon atoms, r and z are integers hav-- ing a value of from zero to 4, inclusive, and R is repre- 2,2-bis( 4-hydoxyphenyl )propane,  
 2,4-dihyroxydiphenyl-methane.  
 bis-( 2-hydroxyphenyl )methane,  
 bis-(4-hydroxyphenyl)methane,  
 bis-(4-hydroxy-2,6-dimethyl-3- methoxyphenyhmethane,  
 ,l-bis-( 4-hydroxyphenyl )ethane,  
 ,2-bis-(4-hydroxyphenyl)ethane.  
 ,l-bis-(4-hydroxy-2chlorophenyl)ethane,  
 1-bis-(3-methyl-4-hydroxyphenyl)propane,  
 3-bis-( 3-methyl-4-hydroxyphenyl )propane,  
 2,2-bis-(3-phenyl-4-hydroxyphenyl)propane,  
 2 ,2-bis-( 3-isopropyl-4-hydroxyphenyl )propane,  
 2,2-bis-( 2-isopropyl-4-hydroxyphenyl )propane,  
 2,2-bis-(4-hydroxynaphthyl)propane,  
 -bis-(4-hydroxyphenyhpentane.  
 3-bis-(4-hydroxyphenyl)pentane,  
 2,2-bis-( 4hydroxyphenyl )heptane bis-(4-hydroxyphenyl)phenylmethane,  
 2,2-bis-(4-hydroxyphenyl)-l-phenylpropane, 2,2-bis(4-hydroxyphenyl)-l l l .3,3,3,-hexafluoropropane and the like;  
 Di(hydroxyphenyl)sulfones such as bis-(4-hydroxyphenyl)-sulfone, 2,4&#39;-dihydroxydiphenyl sulfone, 5&#39;-chloro-2,4&#39;-dihydroxydiphenyl sulfone, 5&#39;- chloro-4,4&#39;-dihydroxydiphenyl sulfone, and the like;  
 -Di(hydroxyphenyl)ethers such as bis-(4- hydroxyphenyl)-ether, the 4,3&#39;-, 4,2&#39;-, 2,2&#39;-, 2,3-  
 dihydroxydiphenyl ethers, 4,4 &#39;-dihydroxy-2,6- dimethyldiphenyl ether, bis-(4-hydroxy-3- isobutylphenyl )ether, bis-(4-hydroxy-3- isopropylphenyl )ether, bis-(4-hydroxy-3- chlorophenyl )-ether, bis-(4-hydroxy-3- fluorophenyl )ether, bis-(4-hydroxy-3- bromophenyl )ether, bis-( 4-hydroxynaphthyl ether, bis-(4-hydroxy-3-chloronaphthyl)ether, 4,4- &#39;-dihydroxy-3,o-dimethoxydiphenyl ether, 4,4- dihydroxy-2,S-diethoxydiphenyl ether, and like materials.  
  It is also contemplated to use a mixture of two or more different dihydric phenols to accomplish the same ends as above. Thus, when referred to above, the E residuum in the polymer structure can actually be the same or different aromatic residua.  
  As used herein, the E term defined as being the residuum of the dihydric phenol&#34; refers to the residue of the dihydric phenol after the removal of the two aromatic hydroxy groups. Thus, it is readily seen that polyarylene polyethers contain recurring groups of the residuum of the dihydric phenol and the residuum of the benzenoid compound bonded through aromatic ether oxygen atoms.  
  The residuum E of the benzenoid compound can be from any dihalobenzenoid compound or mixture of dihalobenzenoid compounds which compound or compounds have the two halogens bonded to bnezene rings having an electron withdrawing group in at least one of the positions ortho and para to the halogen group. The dihalobenzenoid compound can be either mononuclear where the halogens are attached to the same benzenoid ring or polynuclear where they are attached to different benzenoid rings, as long as there is the activating electron withdrawing group in the ortho or para position of that benzenoid nucleus.  
  Any of the halogens may be the reactive halogen substituents on the benzenoid compounds, fluorine and chlorine substituted benzenoid reactants being preferred.  
  Any electron withdrawing group can be employed as the activator group in the dihalobenzenoid compounds. Preferred are the strong activating groups such as the sulfone group (S0 bonding two halogen substituted benzenoid nuclei as in the 4,4&#39;-dichlorodiphenyl sulfone and 4,4&#39;-difluorodiphenyl sulfone, although such other strong withdrawing groups hereinafter mentioned can also be used with ease. It is further preferred that the ring contain no electron supply groups on the same benzenoid nucleus as the halogen; however, the presence of other groups on the nucleus or in the residuum of the compound can be tolerated. Preferably, all of the substituents on the benzenoid nucleus are either hydrogen (zero electron withdrawing), or other groups having a positive sigma value, as set forth in J. F. Bunnett in Chem. Rev., 49,273 (1951) and Quart. Rev., 12,1 (1958).  
  The electron withdrawing group of the dihalobenzenoid compound can function either through the resonance of the aromatic ring, as indicated by those groups having a high sigma value, i.e., above about +0.7 or by induction as in perfluro compounds and like electron sinks.  
  Preferably the activating groups should have a high sigma value, preferably above 1.0, although sufficient activity is evidenced in those groups having a sigma value above 0.7.  
  The activating group can be basically either of two types:  
  a. monovalent groups that activate one or more halogens on the same ring as a nitro group, phenylsulfone, or alkylsulfone, cyano, trifluoromethyl, nitroso, and hetero nitrogen as in pyridine.  
  b. divalent groups which can activate displacement of halogens on two different rings, such as the sulfone group -SO the carbonyl group -CO the vinyl group -CHCH; the sulfoxide groups SO the azo group N=N; the saturated flurocarbon group.  
 organic phosphine oxides where R is a hydrocarbon group; and the ethylidene group X-C-X where X can be hydrogen or halogen or divalent groups which can activate halogens on the same ring such as with diflurobenzoquinone, 1,4- or 1,5- or 1,8- difluoroanthraquinone.  
  If desired, the polymers may be made with mixtures of two or more dihalobenzenoid compounds each of which has this structure, and which may have different electron withdrawing groups. Thus, the E residuum of the benzenoid compounds in the polymer structure may be the same or different.  
  It is seen also that as used herein, the E term defined as being the residuum of the benzenoid compound refers to the aromatic or benzenoid residue of the compound after the removal of the halogen atoms on the benzenoid nucleus. Suitable polysulfones are described in U.S. Pat. No. 3,365,517, particularly columns 2-6 thereof, incorporated by reference herein.  
  6. Also suitable are epoxy resins formed from polyepoxides and an epoxy curing agent. The polyepoxide may be any material having more than one epoxy group, i.e., more than one group, an epoxy quivalency per 100 grams greater than 0.20 as determined by standard analysis, and preferably a molecular weight below 900. These polyepoxides may be saturated or unsaturated and aliphatic, cycloaliphatic and aromatic and may be substituted with substituents, such as chlorine atoms, hydroxyl groups, alkoxy radicals and the like.  
  Examples of these polyepoxides include, among others, vinyl cyclohexene dioxide, 2,3,5,6-diepoxyoctane, 2,3 ,6,7-diepoxydodecane, l,2-epoxy-3-(2,3- epoxypropyl) cyclohexane, l,2-epoxy-4-epoxybutyl)- cyclohexane, epoxidized triglycerides such as epoxidized glycerol trioleate and epoxidized glycerol trilinoleate, the monoacetate of epoxidized glycerol dioleate bis-(2,3-epoxycyclopentyl)ether, and the like.  
  Other polyepoxides comprise the polyepoxy polyethers obtained by reacting, preferably in the presence of an acid-acting compound, such as hydrofluoric acid, one of the aforedescribed halogen-containing epoxides with a polyhydric alcohol, and subsequently treating the resulting product with an alkaline component. As used herein and in the claims, the expression polyhydric alcohol&#34; is meant to include those compounds having at least two free alcoholic OH groups and includes the polyhydric alcohols and their ethers and esters, hydroxy-aldehydes, hydroxy-ketones, halogenated polyhydric alcohols and the like.  
  Polyhydric alcohols that may be used for this purpose may be exemplified by glycerol, propylene glycol, ethylene glycol, diethylene glycol, butylene glycol, hexanetriol, sorbitol, mannitol, pentaerythritol, polyallyl alcohol, polyvinyl alcohol, inositol, trimethylopropane, bis( 4-hydroxycyclohexyl )dimethylmethane, 1,4- dimethylolbenzene, 4,4&#39;-dimethyloldiphenyl, dimethyloltoluenes, and the like. The polyhydric ether alco hols include, among others, diglycerol, triglycerol, dipentaerythritol, tripentaerythritol, dime thylolanisoles, beta-hydroxyethyl ethers of polyhydric alcohols, such as diethylene glycol, polyethylene glycols, bis(beta-hydroxyethyl ether) of bis-phenol, betahydroxyethyl ethers of glycerol, pentaerythritol, sorbitol, mannitol, etc., condensates of alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, glycidyl, epichlorohydrin, glycidyl ethers, etc., with polyhydric alcohols, such as the foregoing and with polyhydric thioesters, such as 2,2- dihydroxy diethyl sulfide, 2,2-3,3 &#39;-tetrahydroxy dipropyl sulfide, etc. The hydroxy-aldehydes and ketones may be exemplified by dextrose, fructose, maltose, glyceraldehyde. The mercapto (thio) alcohols may be exemplified by alpha-monothioglycerol, alpha, alphadithioglycerol, etc. The polyhydric alcohol esters may be exemplified by monoglycerides, such as monostearin, monoesters of pentaerythritol and acetic acid, butyric acid, pentanoic acid, and the like. The halogenated polyhydric alcohols may be exemplified by the monochloride of pentaerythritol, monochloride of sorbitol, monochloride of mannitol, monochloride of glycerol, and the like.  
  Coming under special consideration are the polygycidyl polyethers of polyhydric alcohols obtained by reacting the polyhydric alcohol with epichlorohydrin, preferably in the presence of 0.1 to 5 by weight of an acid-acting compound, such as boron trifluoride, hydrofluoric acid, stannic chloride or stannic acid. This reaction is effected at about 50 to C with the proportions of reactants being such that there is about one mole of epichlorohydrin for every equivalent of hydroxyl group in the polyhydric alcohol. The resulting chlorohydrin ether is then dehydrochlorinated by heating at about 50 to 125 C with a small, e.g., 10%, stoichiometrical excess of a base, such as sodium aluminate.  
  The products obtained by the method shown in the preceding paragraph may be described as polyether polyepoxide reaction products which in general contain at least three non-cyclic ether (0 linkages, terminal epoxide-containing ether.  
  0 dama e...)  
  These halogen-containing polyether polyepoxide reaction products obtainable by partial dehydrohalogenation of polyhalohydrin alcohols may be considered to have the following general formula in which R is the residue of the polyhydric alcohol which may contain unreacted hydroxyl group, Y indicates one or more of the epoxy ether groups attached to the alcohol residue, y may be one or may vary in different reaction products of the reaction mixture from zero to more than one, and Z is one or more, and X Z, in the case of products derived from polyhydric alcohols containing three or more hydroxyl groups, averages around two or more so that the reaction product contains on the average two or more than two terminal epoxide groups per molecule.  
  The epoxy curing agent employed in the impregnating solution may be any alkaline, neutral or acidic compound which acts to effect cure of the polyepoxide to form an insoluble product. The epoxy curing agent is preferably neutral or alkaline. Examples of curing agents include, among others, alkalies like sodium or potassium hydroxides; alkali phenoxides like sodium phenoxide; carboxylic acids or anhydrides, such as formic acid, oxalic acid or phthalic anhydride; Friedel Crafts metal halides like aluminum chloride, zinc chloride, ferric chloride or boron trifluoride as well as complexes thereof with ethers, acid anhydrides, ketones,  
 diazonium salts, etc.; salts such as zinc fluoborate, magnesium perchlorate and zinc fluosilicate; phosphoric acid and partial esters thereof including n-butyl orthophosphate, diethyl ortho-phosphate and hexethyl tetraphosphate, amino compounds, such as, for example, diethylene triamine, triethylene tetraamine, dicyandiamide, melamine, pyridine, cyclohexylamine, benzyldimethylamine, benzylamine. diethylaniline, triethanolamine, piperidine, tetramethyl piperazine, N,N-dibutyl-1,3-propane diamine, N,N-diethyll ,3- propane diamine, l,2-diamino-2-methylpropane,  
 wherein R is a monovalent hydrocarbon radical and R is a bivalent hydrocarbon radical containing no more than 18 carbon atoms and n is an integer, preferably from 1 to 8. Particularly preferred are the aliphatic polyamines having a molecular weight below 250.  
  Suitable polyepoxides are described in U.S. Pat. No. 2,902,398, incorrorated herein by reference.  
  7. Also suitable are both thermoplastic and thermosetting polyesters. Suitable thermoplastic polyesters are condensation polymers of dihydric alcohols with organo-dibasic acids, particularly dicarboxylic acids, and self-condensation polymers of omega-hydroxy carboxylic acids, the preferred materials being poly(ethylene terephthalate), poly(ethylene terephthalateisophthalate), and poly(l,4-cyclohexylenedimethylene terephthalate). Applicable are all filmand fiber-forming polyesters, in which the ester linkages are intralinear, including poly(alkylene alkanedioates), poly(cycloalkylenedimethylene alkanedioates), poly(alkylene arenedioates), poly(cycloalkylenedimethylene arenedioates), and analogous materials. Examples of the abovenamed polyesters are respectively, poly(ethylene adipate), poly(l,4-cyclohexylenedimethylene adipate), poly(ethylene terephthalate and poly( 1,4- cyclohexylenedimethylene terephthalate). Suitable thermoplastic polyesters are described in U.S. Pat. No. 3,410,749, incorporated herein by reference.  
  7a. The thermosetting polyesters are mixtures of unsaturated polyester resins with copolymerizable ethylenically unsaturated monomers. Under the influence of various catalytic or promoting substances, these resinlike materials can be converted into solid, insoluble and infusible shapes. This transformation is essentially a co polymerization of the unsaturated polyester with the added monomer, leading to a cross-linked polymer of exceedingly high molecular weight.  
  The unsaturated polyester resin may be defined as a self-condensation product of an ester of a polyhydric alcohol with a polycarboxylic acid, at least one of which is unsaturated. Frequently the unsaturated poly ester is made from one or more glycols and one or more alpha, beta-ethylenically unsaturated polycarboxylic acids. By way of non-limiting example, it may be mentioned that polyesters can be prepared from such acids as maleic, fumaric, aconitic, mesaconic, citraconic, ethylmaleic, pyrocinchoninic, veronic, or itaconic acid (with or without such acids as adipic, succinic, sebacic, phthalic, etc., or such acids as linolenic, linoleic, elaeosteric, etc.) with such glycols as ethylene, diethylene, triethylene, polyethylene, 1,3-propylene, 1,2- propylene, dipropylene (1,3 or 1,2), butylene or styrene glycol.  
  The copolymerizable ethylenically unsaturated monomers suitable for mixing with the foregoing unsaturated polyesters to produce the desired thermosetting composition are also well-known. Among the more important of such monomers may be mentioned styrene, vinyl toluene, methyl methacrylate, vinyl acetate, diallyl phthalate and triallyl cyanurate. Suitable thermosetting polyesters are described in U.S. Pat. No. 3,267,055, incorporated herein by reference.  
  8. Further suitable polymers are polycarbonates which may be prepared by reacting a dihydric phenol with a carbonate precursor such as phosgene, a haloformate, or a carbonate ester. Generally speaking, such carbonate polymers can be typified recurring structural units of the formula F B 0.3.. T J  
 where B is divalent aromatic radical of the dihydric phenol employed in the polymer producing reaction. The dihydric phenols which may be employed to provide such aromatic carbonate polymers are mononuclear or polynuclear aromatic compounds, containing as functional groups, two hydroxy radicals, each of which is attached directly to a carbon atom of an aromatic nucleus.  
 Typical dihydric phenols are 2,2-bis-(4-hydroxyphenyl)propane,  
 hydroquinone,  
 resorcinol,  
 2,2-bis-(4-hydroxyphenyl) pentane,  
 2,4-dihydroxy diphenyl methane,  
 bis-( 2-hydroxyphenyl )methane,  
 bis-( 4-hydroxyphenyl )methane,  
 bis-(4-hydroxy-5-nitrophenyl)methane,  
 l,l-bis-(4-hydroxyphenyl)ethane,  
 3,3-bis-(4-hydroxyphenyl)pentane,  
 2,2&#39;-dihydroxydiphenyl,  
 2,6-dihydroxy naphthalene,  
 bis-( 4-hydroxyphenyl )sulfone,  
 2,4-dihydroxydiphenyl sulfone,  
 5&#39;-chloro-2,4-dihydroxydiphenyl sulfone,  
  17 bis-(4-hydroxyphenyl)diphenyl disulfone, 4,4-dihydroxyphenyl ether, 4,4-dihydroxy-3,3-dichlorodiphenyl ether, and 4,4-dihydroxy-2,S-diethoxydiphenyl ether.  
  A variety of additional dihydrophenols which may be employed to provide such carbonate polymers are disclosed in US. Pat. No. 2,999,835. It is, of course, possible to employ two or more different dihydric phenols, or a dihydric phenol in combination with a glycol, a hydroxy terminated polyester, or a dibasic acid in the event a carbonate copolymer rather than a homopolymer is desired for use in the preparation ofthe mixtures of the invention.  
  When a carbonate ester is used as the carbonate precursor in the polymer forming reaction, the materials are reacted at temperatures of from 100 C. or higher for times varying from 1 to hours. Under such conditions ester interchange occurs between the carbonate ester and the dihydric phenol used. The ester interchange is advantageously consummated at reduced pressures of the order of from about 10 to about 100 mm. of mercury, preferably in an inert atmosphere, such nitrogen or argon, for example.  
  Although the polymer forming reaction may be conducted in the absence of a catalyst, one may, if desired, employ the usual ester exchange catalysts, such as, for example, metallic lithium, potassium, calcium and magnesium. Additional catalysts and variations in the exchange methods are discussed in Groggins, Unit Processes in Organic Synthesis (4th edition, McGraw-Hill Book Company, 1952), pages 616 to 620. The amount of such catalyst, if used, is usually small, ranging from about 0.001 to about 0.1%, based on the moles of the dihydric phenol employed.  
  The carbonate ester useful in this connection may be aliphatic or aromatic in nature, although aromatic esters, such as diphenyl carbonate, are preferred. Additional examples of carbonate esters which may be used are dimcthyl carbonate, diethyl carbonate, phenyl methyl carbonate, phenyltolyl carbonate and di(tolyl) carbonate. Suitable polycarbonates are described in US. Pat. No. 3,365,517, particularly columns 6 and 7.  
  9. Additionally suitable are cellulose esters and nitrocellulose based coatings including cellulose acetate, cellulose acetate propionate, cellulose acetate butyrate. ethyl cellulose, cellulose nitrate, etc. Cellulose acetate esters are prepared by the reaction of chemical cellulose with acetic acid and acetic anhydride, sulfuric acid generally being used as a catalyst. Ethyl cellulose is an ether and manufactured by the reaction of chemical cellulose with caustic to form alkali cellulose, which then reacts with ethyl chloride to form ethyl cellulose. Cellulose nitrate is also referred to as nitrocellulose and is prepared by the nitration of chemical cellulose, using sulfuric acid as catalyst and dehydrating agent,  
  10. Formaldehyde resins, for example, phenol formaldehyde resins and urea-formaldehyde resins as described in The Encyclopedia of Polymer Science and Tet/urology, lnterscience, 1969 Edition, Volume 10, pages 1-73 and Volume 2, pages 25 -42, respectively.  
  1 l. Polyamides including polyaminated derivatives of carboxylic acids, the structural units being corrected by amide or thioamide groupings having the general formula:  
 wherein X is O or S.  
  Such polyamides are generally formed by the reaction of dicarboxylic acids with diamines, such as, adipic acid and hexamethylene diamine, from omega-amino acids, or by a ring opening reaction of lactams such as epsilon-caprolactam. Other suitable fiber forming polyamides are described in Nos. Pat. No. 2,071,250, 2,071,253, 1,130,523 and 2,130,948, incorporated herein by reference.  
  Normally, the amount of fire retardant used depends on the nature of the polymer and the proposed end use. It is thus well within the knowledge of the skilled art worker to select the optimum content of the fire retardant system of the present invention for any given polymer. Generally, however, the amount of fire retardant is sufficient to produce a halogen content in the polymer of preferably from about 1 to 20 percent by weight of the composition and most preferably from about 2 to 13 percent by weight of the composition.  
 EXAMPLE 1 Preparation of l ,2,3,4,9,9-hexachloro-1,4,4a,8atetrahydro- 1 ,4-methanonaphthalene-5 ,8-dione A mixture of 54.6 g. (0.2 mole) of hexachlorocyclopentadiene, 21.6 g. (0.2 mole) of p-benzoquinone, and 10 m1. of toluene were placed in a ml. round bottom flask and heated for three hours so that the toluene refluxed gently. At the end of this period the reaction mixture suddenly solidified completely, indicating completion of the reaction. The crude product was bright yellow. The damp material was transferred to a Buchner funnel, rinsed with absolute ethanol, dried on the funnel, and crystallized from ethanol. 49 g. of bright yellow dense crystals were obtained, m.p. l89-193 C (reported 188 C). The yield was 64%.  
 The product has the following structure:  
  Cl 11 01 l C1 EXAMPLE2 EXAMPLE 3 Preparation of 1,2,3 ,4,9,9-hexachloro-l,4-dihydro-1,4- methanonaphthalene- 1 ,8-dione 38 g. of the diol prepared according to Example 2 were dissolved in 300 ml. of anhydrous ether and 30 g. of anhydrous Na SO and 29 g. of Ag O were added to this solution. The reaction mixture was shaken on a Parr Shaker until the color turned to deep orange (about minutes). Filtration and evaporation of the ether produced an orange colored solid. One recrystallization from hexane-benzene mixture gave organe crystals, mp. 118-119C. The yield was about 70 percent.  
 The product has the following structure:  
 EXAMPLE 4 EXAMPLE 5 Preparation of 1,2,3.4,5,6,7,8,l1,11,12,12- dodecachloro-l,4,4a, 5, 8, 9a-hexahydro-l,4:5,8- dimethanoanthracene-9, 1 O-dione 38 g. of l,2,3.4,9,9,-hexachloro-l,4-dihydro-l,4- methanonaphthalene-S,8-dione prepared in accordance with Example 3 were mixed with 30 g. of hexachlorocyclopentadiene and 30 ml. of toluene, and refluxed for 6 hours. By cooling to room temperature, yellow crystals were formed and were washed with cold Skelly B solvent. One recrystallization from benzenehexane 50/50 mixed solvent gave yellow crystals, m.p. 234-235 C.  
 Calculated Observed Test 1 Test 2 C 29.4% 28.94 28.96 H 0.3 0.52 0.37 Cl 65.3 64.07 64.25  
 The product has the following structure:  
 Cl C1 cl: Cl  
  ll 11 c1 0 c1 c1 EXAMPLE 6 Preparation of 1,2,3,4,5,6,7,8,11,11,12,12-  
 dodecachlorol ,4,5,8-tetrahydro-1 ,415 ,8- dimethanoanthracene-9 ,10-di0l 49 g, of 1,2,3,4,5,6,7,8,11,11,12,12-dodecach1orol,4,4a,5,8 ,9a-hexahydro-1,415,8-dimethanoanthracene-9,10-dione prepared in accordance with Example 5, were dissolved in methanol and a few drops of pyridine were added. When warmed to about 45 C, the yellow solution became colorless and the isomerization was complete. After cooling to 57 C. and filtration, white crystals were obtained. One recrystallization from methanol gave white crystals, m.p. 329 C.  
 Calculated Observed Test 1 Test 2 C 29.47: 29.6 29.7 H 0.3 7: 0.53 0.49 C] 65.3% 64.97 64.04  
 The product had the following structure:  
 EXAMPLE 7 Preparation of 1,2,3,4,5,6,7,8,11,11,12,12- dodecachloro-l,4,5,8,tetrahydro-1,4:5,8- dimethanoanthracene-9 l0-dione 23 g. of l,2,3,4,5,6,7,8,11,11,12,12-dodecach1orol,4,5,8-tetrahydr0- 1 ,4:5 ,8-dimethanoanthracene-9, l 0- diol, prepared in accordance with Example 6, were dissolved in ml. of anhydrous ether. Anhydrous sodium sulfate, 10 g., and 12 g. of silver oxide were added and the mixture was shaken for 2 hours (Parr shaker). After filtration, the deep red ether solution was evaporated and crude red crystals were obtained. One recrys- Calculated Observed Test 2 64.50  
 Test 1 The product has the following structure:  
  ll IL EXAMPLE 8 Preparation of 6-tert-butyl-l,2,3,4,9,9-hexachlorol.4.4u,8a-tetrahydro-l ,4-methanonaphthalene-5,8- dione 30 g. of tert-butylhydroquinone (Eastman-Kodak) were dissolved in 200 ml. of anhydrous ether and 30 g. of anhydrous sodium sulfate were added. To this mixture was added 60 g. of silver oxide in small increments. An exothermic reaction ensued. After shaking for 20 minutes. the reaction was filtered and the filtrate evaporated under the hood. Yellow crystals of tert-butyl-pbenzoquinone were obtained melting at 5560 C.  
  Hexachlorocyclopentadiene, 40 g., and 15.4 g. of tcrt-butyl-p-benzoquinone were dissolved in 300 ml. of toluene and refluxed for 4 hours. The solution solidifled upon cooling to room temperature. The solid was washed with methanol and recrystallized from benzene. Yellow crystals were obtained, melting at l24-l25 C.  
 Calculated Observed The product has the following structure:  
  0 c1 v C1 me I l Cl uic-c&#39; Cl 11 i EXAMPLE9 dium bicarbonate were added in small increments. The reaction mixture exothermed to 40 C. After 1 hour, the reaction mixture turned almost white. On pouring this solution into water, a pale yellow precipitate was obtained. One recrystallization from methanol gave pale yellow crystals, m.p. l57-159 C. The infrared spectrum showed no carbonyl and weak absorption at 1.610 cm which may be assigned as a C=N bond.  
 The product has the following structure:  
 Preparation of 6-(p-chlorophenylsulfonyl)-l,2,3,4,9,9- hexachloro-l ,4-dihydrol ,4-methanonaphthalene-5 .8- diol 38 g. of l,2,3,4,9,9-hexachloro-1,4-dihydro-l,4- methanonaphthalene-l,8-dione, prepared as in Example 3, were dissolved in 200 ml. of benzene and 20 g. of freshly generated p-chlorobenzenesulfonyl chloride were added. This mixture was refluxed until the orange color disappeared completely (5 hours) and a white precipitate formed. The white solid was filtered off while hot and was recrystallized from benzene yielding white crystals, mp. 21 l2l2 C.  
 Calculated Observed Cl 44.671 Cl 5 5 .771 S This reaction was repeated using ethanol rather than benzene as the solvent. An identical product was obtained.  
 The product has the following structure:  
 OH Cl 1 0 EXAMPLE 1 1 Calculated Observed Cl 42.3% 42.3% S 6.27! 6. [7r  
 The product has the following structure:  
 Preparation of l,2,3.4,9,9-hexachlorol ,4-dihydro-5.8- dihydroxy-l .4-methanonaphth-6-yl methyl ketone 76 g. of l,2.3.4,9,9-hexachlorol ,4-dihydrol .4- methanonaphthalene-S,8-diol, prepared according to Example 2. were suspended in 100 ml. of acetic acid and then 20 ml. of boron trifluoride-diethyl ether complex were added. This mixture was heated at ll05 C for hours. After being cooled to 40 C. the mixture was poured into ice water. After repeated recrystallization from benzene white crystals were obtained, m.p. l35-l40 C.  
  Nmr showed one aromatic proton at 664 Hz as a singlet. two OH protons at 601 and 583 Hz as a singlet. and three acetyl protons at 226 Hz as a singlet. Infrared spectrum showed a strong phenolic OH group and the carbonyl at 1.750 cm.  
 Calculated Observed The product has the following structure:  
 Calculated Observed Test l Test 2 CI 41.2% 421071 4l.7571  
 The product has the following structure:  
 Cl Cl EXAMPLE 14 Preparation of l.2 3.4.9,9-hexachlorol ,4-dihydro-8- methoxyl ,4-methanonaphth-5yl-dim ethyl phosphate 20 g. of 1.2.3.4.).9-hexachloro-l.4-dihydro-l,4- methanonaphthalene-S.8-dione, prepared as in Example 3. were dissolved in ml. of dried benzene and 14 g. of distilled trimethylphosphate were added slowly (exothermic) to the solution so that the temperature was maintained at about 50 C. When the addition was completed. the mixture turned dark but then turned yellow after 30 minutes of additional stirring. When benzene solvent was evaporated, a pale yellow solid was obtained. One recrystallization from benzene- Skelly B (50/50) mix-solvent gave white crystals, m.p. l49-l50 C. Infrared showed no hydroxyl or carbonyl group.  
  Nmr spectrum showed three methoxy protons at 394 Hz and six methoxy protons at 383 Hz. The total yield was about 65%.  
 C ulculuted Obsered CI 42.3% CI 42.5% P 6. 16 P 6.35  
 The product has the following structure:  
 EXAMPLE 15 Preparation of l,2,3,4.9,9-hexachloro-5,8-diethoxyl .4-dihydro-1,4-methanonaphthalene EXAMPLE 17 Preparation of l,2,3,4,9,9-hexachloro-1,4-dihydro-l ,4- methanonaphth-5,8-ylene propionate 18 g- Of ,2,3. -h a hl r -l, -d y 80 g. of l,2,3,4,9,9-hexachloro-l,4-dihydro-l,4- mcthanonaphthalene-S.8-diol, prepared as in Example 5 methan0naphthalene-5,8-di0l, prepared in accordance 2 and 8 g. of NaOH were mixed in 200 ml. of distilled with Example 2, were mixed with 80 g. ofpropionic anwatcr. The diol dissolved readily, forming the sodium hydride and then a few drops of concentrated H 50 Salt- Whlle l an exfiess of ethylbromide W35 were added. As soon as the H 80 was added the mixadded n irrmg was continued for 24 hOurS- A White ture solidified. The thus formed white solid was filtered precipitate was filtered off. One recrystallization from 10 f excess r pionic anhydride on a Buchner funnel methanol resulted in White crystals, -P- C and washed twice with water on the funnel. This solid (yie d abou Infrared analysis ed no ca was recrystallized from benzene and white needlelike bonyl or y y p crystals were obtained, mtp. 204-205 c. The yield was almost quantitative. l5  
 Calculated Observed Test I Test 2 Calculated Observed CI 424%, 49.3% 49.0% Test 1 Test 2 The product has the following structure:  
 The product has the following structure:  
 l C1 o d-011mm 1 Cl 01 c1 o1 -i l &#34;l )CQlI5 bl (|)-CCI&#39;IQCHH EXAMPLE 16 ll Preparation of l,2,3,4,9,9-hexachloro-l,4-dihydro-l,4- EXAMPLE 18 mcthanonaphth-S,8-ylcne acetate 7 20 of 1Q2Q34 99 heXaCh]OrO 1,4 dihydm 1,4 Preparation of l,2,3,4,9,9-hexachloro-l,4-d1hydromethanonaphthalene-S,8-diol, prepared as in Example dlhydro&#39;l P -y decafloate 2. were mixed with 25 g. of acetic anhydride and 38 of &#39;b m cooled by a water bath and then one drop of concen- 40 metha&#34;n al mha1e ne-5341101 prePared as m Example trated H 50 was added. The reaction was exothermic were dlssolved 150 of dried benzene 38 and the reaction mixture instantly solidified. One reof decanoyl Chlorlde addefl Slowly under crvstallization from benzene/methanol mixture gave T P F- The mlxture was heatFd at white crystals, m.p. 252-253 C. The yield was essem 70 75 C. unt1ll-lCl evolution ceased. After cooling to tially quantitative. Infrared analysis showed ester carroom tempemulreithe benzene was eiaporated under bonyl and no hydroxyl group vacuum and a l1qu1d product was obtained.  
 Calculated Observed I I Test 1 Test 2 Calculated Obsened CI 3177 2998 3006 Test l Test 2 CI 45.9%; 46.23 451987! The product has the following structure:  
 The product has the following structure: I ll o-c-(cfimom C1 Cl 01 V 0 01 o c c1n ml c1 01 (1 (!)-(|f(CHz)aCII;  
  C1 1 EXAMPLE 19 Preparation of l,2,3,4,9,9-hexachlorol ,4-dihydr0-l ,4- methanonaphth-5,8-ylene pivalate To a mixture of 38 g. of l,2.3.4.9,9-hexachloro-l,4- dihydro-l ,4-methanonaphthalene- .8-diol, prepared as in Example 2, and 16 g of pyridine in 200 ml. of dry benzene, 24 g. of pivaloyl chloride were added from a dropping funnel. After 4 hours heating at 60-70 C. the mixture was cooled to room temperature and the white pyridinium salt was filtered off. Evaporation of the benzene resulted in a white solid. This solid was recrystallized from benzene-Skelly B mixed solvent yielding white crystals, m.p. l34l 35 C.  
 Calculated Observed The product has the following structure:  
  CH3 0 C1 C1 cage-liq C1 cHi -c1 on: CH O-C-( ll CH3 0 EXAMPLE 20 Preparation of l,2,3,4,9,9-hexachlorol .4-dihydronaphth 5.8-ylene trichloroacetate 38 g. of l,2,3,4,9,9-hexachloro-l,4-dihydro-l,4- dimethanonaphthalene-S,S-diol, prepared as in Example 2, 16 g. of pyridine, and 200 ml. of dry benzene were mixed, and 40 g. of trichloroacetylchloride were added slowly to the mixture from a dropping funnel. After 4 hours heating at 60-70 C. the mixture was cooled to room temperature and the white pyridinium salt was filtered off. Evaporation of the benzene resulted in a white solid. This solid was recrystallized from benzene-Skelly B mixed solvent yielding white crystals, m.p. l35l36 C. The yield was about 60% after recrystallization. Nmr showed only one singlet at 718 Hz. Infrared showed carbonyl at 1,790 cm and no OH group. Chlorine analysis showed:  
 Calculated Observed The product has the following structure:  
 EXAMPLE 2] Preparation of l,2.3,4,9,9-hexachlorol .4-dihydrol .4- methanonaphthalene-S,6,8-triyl acetate 20 g. of l.2,3,4,9.9-hexachloro-l,4-dihydro-l,4- methanonaphthalene-5,8-dione, prepared as in Example 3, were mixed with 20 ml. of acetic anhydride, and 3 ml. of concentrated H 50 were added to the mixture. The mixture was then stirred vigorously at 90 C. until the orange color disappeared. After cooling to room temperature, the formed white solid was filtered on a Buchner funnel and washed twice with water. This solid was recrystallized from ethanol and white crystals were obtained, m.p. l79-l 80 C. Total yield was about Nmr showed 2 protons (aromatic) at 687.5 Hz, 6 protons (methyl) at 227.5 Hz, and 3 protons (methyl) at 222 Hz, all as singlets. Infrared analysis showed one carbonyl at 1.775 cm and no OH group.  
 Calculated Observed The product has the following structure:  
 EXAMPLE 22 Preparation of 2,2&#39;-( l,2,3,4,9,9-hexachloro-l ,4- dihydro-l ,4-methanonapth-5,8-ylenedioxy)diethanol NaOH (10 g.) was dissolved in 200 ml. of distilled water and then 38 g. of l,2,3,4,9,9-hexachloro-l,4- dihydrol.4-methanonaphthalene-5,8-diol, prepared according to Example 2, were added as quickly as possible under nitrogen flow. The diol dissolved readily and then 34 g. (large excess) of chloroethanol were added and the mixture was heated at 50-60 C. for 12 hours. As the reaction proceeded, a white precipitate formed. This white solid was filtered and washed with water twice. Repeated recrystallization from watermethanol (50/50) mix-solvent gave white crystals, m.p. l50-l5l C. The yiedld was about 65%.  
 The product has the following structure:  
 HOCHzCHzO C1 l l Ll OCH2CII201I EXAMPLE 23 Preparation of 5,8-diallyloxy-l,2,3,4,9,9-hexachlorol ,4-dihydrol .4-methanonaphthalene NaOH (20 g.) was dissolved in 300 ml. of watermethanol mix solvent (200/100) and nitrogen was bubbled through the solution for 20 minutes. 80 g. o l.2.3.4.9,9-hexachloro-1.4- dihydrol ,4-methanonaphthalene-4,8-diol, prepared as in Example 2, were quickly added under nitrogen flow. While stirring, 40 g. of allylbromide were added at one time. A slight exothermic reaction was observed. This reaction mixture was heated at 5060 for 6 hours. When cooled in an ice water bath, a dark colored solid was obtained. Repeated recrystallization from methanol gave white crystals, m.p. ll4l 15 C. The yield after the recrystallization was poor (about 30%). Nmr showed two aromatic protons at 677 Hz as a singlet, six olefinic protons at 615-519 Hz as a complicated multiplet. and four methylene protons at 452.2 447.5 Hz as a multiplet. lnfrarcd analysis showed no -OH group:  
 Elemental Analysis: Calculated Observed Carbon 44.2% 43.6% Hydrogen 2.6 2.5 Chlorine 46.2 45.5  
 The product has the following structure:  
 O-CHz- CH=CH3 EXAMPLE 24 342.6 grams (82.5% oftheory). M.P. l75-l77C. The 55 product has the following structure:  
  or H w l 01 EXAMPLE 25 Preparation of l,2.3,4,o.9.9-heptachloro-l.4dihydrol.4-methanonaphthalene-5 ,8-diol A mixture of 256 grams l,2,3,4,6,9,9- heptachloro- 1 ,4,4a,8a-tetrahydro-l ,4-methanonaphthalene-5,8-dione, prepared according to Example 24, and 500 ml. of methanol in a 2 liter reaction flask was stirred at room temperature while air in the reaction vessel was swept out with nitrogen. Six ml. of pyridine was then added to the liquid-solid mixture. The resulting reaction mixture was continuously stirred, and refluxed vigorously for 8.5 hours. After cooling the mixture to 0 C., it was filtered, and the crude solid was washed with cold Skellysolve. Yield 12] grams. The product was recrystallized from a mixture of 1000 ml. of Skellysolve and 250 ml. of acetone. M.P. l20.5-l22 C. The product has the following structure:  
 (0.62 mol.) of  
 OH 01 C1 C1 G1 I (51 EXAMPLE 26 Preparation of l,2,3,4,6,9,9-heptachloro-1,4-dihydrol,4-methanonaphth-5,8-ylene acetate 23 g. of l,2,3,4,6,9,9-heptachloro-1,4-dihydro-l,4- methanonaphthalene-S,8-diol, prepared as in Example 25, were mixed with 25 g. of acetic anhydride. The mixture was cooled in a water bath and then one drop of concentrated H SO was added. The reaction was exothermic and the reaction mixture instantly solidified. Recrystallization from benzene/methanol solvent gave white crystals, m.p. l-l62 C. The yield was essentially quantitative.  
 Calculated Observed The product has the following structure:  
 hexachloro-l ,4-dihydro-l ,4-methanonaphth-5 ,8-ylene acetate 30 g. of 6-(p-chlorobenzenesulfonyl)-l,2,3,4,9,9- hexachlorol ,4-dihydrol ,4-methan0naphthalene-5 ,8-  
  diol, prepared as in Example 10, were mixed with 40 ml. of acetic anhydride and a few drops of concentrated H were added. As soon as the H 80 was Calculated Observed Test l Test 2 Cl 38.77: 38.54 38.78 7: S 5.0 4.46 4.58  
 The product has the following sturcture:  
  l) o-dcm l m c1 EXAMPLE 28 Preparation of 1.2.3.4.).9-hexachlorol .4-dihydrol .4- methanOnaphthiS-ylene butylcarbamate 38 g. of l.2.3.4,9.9-hexachloro-l,4-dihydro-l.4- mcthanonaphthalene-S.8-diol. prepared as in Example 2, were dissolved in 200 ml. of dry benzene and 25 g. of -n-butyliso-cyanate and then a few drops of triethylamine were added. The reaction mixture was then heated at 7075 C. for 3 hours. After cooling to room temperature. a white precipitate was formed and was filtered off on a Buchner funnel. This white solid was insoluble in benzene and melted at l-202 C.  
 Calculated Observed The product has the following structure:  
 Preparation of l,2,3.4,9.9-hexachlorol .4-dihydrol .4- methanonaphth-S.8-ylene diethyl carbonate 38 g. of l.2,3.4.9,9-hexachlorol .4-dihydrol ,4- methanonaphthalene-S,S-diol. prepared as in Example 2. were dissolved in a mixture of 200 ml. of dry benzene and 16 g. of pyridine. Then g. of chloroethyl carbonate were added slowly. An exothermic reaction ensued.  
 This reaction mixture was heated under gentle reflux of benzene. After 6 hours the reaction mixture was cooled to room temperature and the pyridinium salt formed was filtered off. Evaporation of benzene resulted in a white solid. This solid was recrystallized from hexanebenzene mixed solvent and yielded white crystals, m.p. l l6l 17 C.  
 Calculated Observed The product had the following structure:  
 EXAMPLE 30 Preparation of l,2,3,4,9,9-hexachloro-l.4-dihydro-8- hydroxyl .4-methanonaphth-5-yl p-chlorophenylsulfonate 38 g. of l,2.3,4,9,9-hexachloro-l,4dihydro-1 ,4- dihydro-l .4-methanonaphthalene-5.8-dione. prepared as in Example 3, were dissolved in 200 ml. of benzene and 20 g. of freshly generated p-chlorobenzenesulfinyl chloride was added. This mixture was refluxed until the orange color disappeared completely (5 hours) and a white precipitate formed. The white solid was filtered off. (See Example 10). The filtrate solution was concentrated and dissolved in benzene-Skelly B (50/50) mixed solvent and treated with charcoal. Evaporation of the solvent gave a white solid. This solid was recrystallized from Skelly B-benzene (50/50) solvent yielding white crystals, m.p. l65 C.  
 Calculated Observed Cl 44.67: C] 44.4% S 5.7 S 5.6  
 The product has the following structure:  
  01 or or EXAMPLE 31 Preparation of l,2,3,4,9,9-hexabromo-1,4-dihydro-l ,4- methanonaphthalene-S,8-diol Distilled water (3.34 kg.) was placed in a 5 liter, three-neck, round bottom flack equipped with a stirrer, condenser, thermomether, and cooling bath. Sodium hydroxide (528 g.; 13.2 moles; 100% excess) was added to the water in portions, and the solution was stirred continuously. When the addition was completed and the temperature of the solution was at C. or slightly lower, bromine (527.4g.; 3.3moles; 169 ml.) was added in a fairly rapid stream through a dropping funnel. The temperature of the solution was kept at or somewhat below 0 C. during this addition of bromine. When the addition was completed and the temperature of the hypobromite solution was 2 to 7 C., a (15 to 5 C.) solution of cold, freshly distilled 1,3- cyclopentadiene (33.05 g.; 0.5 mole; 41.07 ml.) in 400 ml. of Skelly-solve was added rapidly over a period of about 5 minutes to the continuously stirred sodium hypobromite solution. When this addition was completed, stirring was continued and the reaction mixture was allowed to warm to about C. The mixture was transferred to a 6 liter separatory funnel and the layers were separated. The aqueous layer was extracted at once with three 500 ml. portions of Skellysolve and the combined extracts were added to the original Skellysolve solution. The resulting solution was thoroughly dried over molecular sieves, filtered, and the filtrate was placed on a steam bath to evaporate solvents. The residual. unrecrystallized l,2,3,4,5,5-hexabromo-1,3- cyclopentadiene (237.3 g.; 88% yield), after recrystallization from cyclohexane, melted at 8788 C.  
  A mixture of benzoquinone, 10.8 g. toluene (40 ml) and 1.2.3 ,4,5,5-hexabromo-l ,3-cyclopentadiene(60 g.) was heated to reflux temperature and refluxed for 4 hours. At the end of this reaction period a dark solid had formed. This solid was placed on a Buchner funnel and washed with Skelly B solvent and a small amount of methanol. The solid was then recrystallized from benzene and white crystals were obtained, m.p. 204-206 C.  
 The product has the following structure;  
 OH Br Br Br Br AH EXAMPLE 32 Calculated Observed Test 1 Test 2 Br 66.9% 65.70 65.21%  
 The product had the following structure:  
  0 O CH3 Br Br O(3CH3 EXAMPLE 33 EXAMPLE 34 Preparation of 1 ,2,3,4,9 ,9-hexachloro-l ,4-dihydrol ,4- methanonaphth-5,8-ylene benzoate 38 g. of 1,2,3,4,9,9-hexachloro-l,4-dihydro-1,4- methanonaphthalene-S,8-diol prepared as in Example 2, 16 g. of pyridine, and 200 ml. of dry benzene were mixed and 28 g. of benzoyl chloride were added slowly to the mixture from a dropping funnel. After 4 hours heating at 60-70 C., the mixture was cooled to room temperature and the white pyridinium salt was filtered off. Evaporation of the benzene resulted in a white solid. This solid was recrystallized from benzene-Skelly B mixed solvent yielding white crystals, m.p. 2l32 15 C. The yield was about 60% after recrystallization.  
 The product has the following structure:  
 EXAMPLE 35 Observed Test 2 Test 1 Calculated The product has the following structure:  
 l c1 c1 4 Y )1 c1 AC1 c1 OSO2CII3 EXAMPLE 36 Preparation of 6-tert-butyll .2,3,4,9,9-hexachlorol ,4- dihydrol .4-methanonaphthalene-5 ,8diol g. of 6-tert-butyl-l.2,3,4,9,9-hexachlorol,4,4a,8a-tetrahydro-l ,4-methanonaphthalene-5,8- dione, prepared according to Example 8, were dissolved in 50 ml. of methanol. A few drops of pyridine were added and the solution was refluxed strongly for 3 hours. Evaporation of the methanol yielded an oily material which upon recrystallization twice from Skelly B gave white needle crystalls melting at 9698 C.  
  Nmr showed nine tert.-butyl protons at l34 Hz as a singlet, two hydroxyl protons at 347 Hz and one aromatic proton at 669 Hz. Infrared spectrum showed strong phenolic -OH group absorption at 3.500 cm and no carbonyl. The product has the following structure:  
  c c1 on c1 CIIg ry H3C EXAMPLE 37 Preparation of 0,0 l ,2,3,4,9,9-hexachloro-1,4-dihydrol,4-methanonaphth-5,8-ylene dimethylthiocarbamate 38 g. of methanonaphthalene-S,S-diol, prepared as in Example 2, and I l g. of triethylamine were dissolved in 300 ml.  
 l,2.3,4,9,9-hexachloro-l ,4-dihydro-l ,4- 6  
 of dry benzene and 25 g. of dimethylthiocarbamoyl chloride were added slowly to the solution. After refluxing strongly for 6 hours the reaction mixture was cooled to room temperature and the salt was filtered off. The benzene solution was washed twice with water and then dried over anhydrous magnesium sulfate. Evaporation of the benzene yielded the crude solid. This solid was recrystallized from benzene and pale yellow crystals were obtained, m.p. ll98 C.  
 The product has the following structure:  
 EXAMPLE 38 Preparation of l,2,3.4,9,9-hexachloro-l ,4,dihydro-l ,4- methanonaphth 5,8-ylene bis(ethylene phosphite) 38 g. of l,2,3,4,9.9-hexachloro-l,4-dihydro-l .4- methanonaphthalene-S.8-diol, prepared as in Example 2, were dissolved in 300 ml. of dry benzene and 26 g. of freshly distilled chloroethylene phosphite were added slowly from a dropping funnel. The reaction mixture was refluxed until no more HCl evolved (6 hours). The solvent was evporated completely under vacuum and a pale yellow waxy material and obtained. Purification was difficult due to the hydrolytic nature of the compound.  
 The product has the following stucture:  
 EXAMPLE 39 Preparation l,2.3,4.9,9-hexachloro-l ,4-dihydro-l ,4- methanonaphth-5,8-ylene 0,0-hydroxybenzoate A mixture 1,2.3.4,9.9-hexachloro-l,4-dihydro-l,4- methanonaphthalene-S,8-diol prepared according to Example 2 (l0.0g.), salicylic acid (7.4 g.), and phosphorus pentachloride (3.6 g.), was heated in refluxing xylene for 2 days. The crystals which formed upon cooling the reaction mixture were separated by filtration. The crude product was recrystallized from benzene-petroleum ether to give a pure sample, m.p. 232233 C. Additional product was obtained by removal of the solvent and recrystallization of the residue from benzene-petroleum ether. Total yield was about 27%.  
 Calculated Observed Test 1 Test 2 The compound has the following structure:  
 Preparation of l,2,3,4,9,9-hexachloro-1,4,4a,6,7,8ahexahydrol ,4-methanonaphthalene-5,8-dione 38 g. of l,2,3,4,9,9-hexachloro-l,4,4a,8a-tetrahydro- 1,4-methanonaphthalene-5,8-dione, prepared as in Example l, were suspended in 150 ml. of glacial acetic acid and then this mixture was poured into 20 g. of zinc dust suspended in 150 ml. of distilled water. A slight exotherm occured during stirring and the temperature was maintained at 50C. for 3 hours by external heating. Then 200 ml. of chloroform were added and stirring was continued for 30 minutes more, The chloroform layer was separated and washed with a saturated sodium carbonate solution and dried over anhydrous magnesium sulfate. Evaporation of the chloroform left a white solid. One recrystallization from methanol gave white crystals, m.p. l69-l70 C. Infrared spectrum showed carbonyl at 1,740 cm&#34;. The nmr indicated two bridgehead protons at 431 Hz (singlet) and four a protons at 303 Hz and 245 Hz (as a multiplet).  
 The product has the following structure:  
  Cl u 0 EXAMPLE 41 Preparation of l,2,3,4,9,9-hexachloro-l,4,4a,6,7,8ahexahydro-6-phenylsulfonyl-1,4-methanonaphthalene- 5,8-dione 38 g. of 1,2,3,4,9,9-hexachloro-1,4,4a,8a-tetrahydro- 1,4-methanonaphthalene-5,8-dione, prepared as in Example 1, were dissolved in 250 ml. of benzene, 15 g. of freshly generated benzene sulfinic acid were added and then a few drops of water were added. This reaction mixture was heated at 4045 C. for 12 hours and then the benzene was evaporated. The white solid residue obtained was recrystallized from benzene twice and yielded white crystals, m.p. l57 l58 C. The yield was about 88%.  
 Calculated Observed Test 1 Test 2 C] 40.9% 39.11 39.63% S 6. l 5.74 5.80  
 The product has the following structure:  
 EXAMPLE 42 Calculated Observed Test 1 Test 2 The product has the following structure: