[1]7 T 21905@697 u niteci 3tates vatetit Office Patented Sept. 22, 1959 2,905,697 CONDENSATION OF COTNJUGATED CYCLOALKA,DIENES WITH P-DIOXFNES AND RESUI;FANT PRODUCTS Louis Schmerling, Riverside, IR., assignor, by mesne assigitments, to Universal Oil Products Conipany, Des Plaines, Ill., a corporation of Delaware No Drawin,-. Application March 5, 1956 10 Serial No. 569,280 14 Claims. (Cl. 260-340.3) This invention relates to new compositions of matter which are prepared by condensing a cycloalkadiene and 15 an unsaturated heterocyclic compound, and more particularly to the condensation products resulting from the reaction between a conjugated cycloalkadiene and a sixmembered unsaturated heterocyclic compound contahiing 20 f,our r-arbon atoms and two non-adjacent oxygen atoms in the ring. It is an object of tWs invention to prepare polycyclic compounds in which one of the rings contains two oxygen atoms. 25 A further object of this invention is to prepare polycyclic. condensation products which are capable of destroying insects. One embodiment of this invention is found in a process whir,h comprises condensing a compound selected from 30 the group consisting of conjugated cycloalkadienes and halo-substituted conjugated cycloalkadienes with a sixmembered unsaturated heterocyclic compound containing four carbon atoms and two non-adjacent oxygen atoms in the ring, and recovering the Tesultant condensation 35 product. A specific embodiment of the invention is found in a process which comprises condensing a polyhalocyclopentadiene with a six-membered unsaturated heterocyclic compound containing four carbon atoms and two non- 40 adjacent oxygen atoms in the ring at an elevated temperature in the range of from about 50' to about 200' C., and recovering the resultant product. A more specific embodiment of the invention resides in a process which comprises condensing a molar pro- 45 portion of hexachlororyclopentadiene with a molar proportion of p-dioxadiene (or, as it is also named, p-dioxin) at an elevated temperatiire in the range of from about 50. to about 250' C., and recovering the resultant 5,6,7,8,9,9- hexachloro - 4a,5,8,ga -,tetrahydro - 5,8 - methanobenzo- 50 p-dioxadiene. Another embodiment of the invention is found in a new composition of matter comprising the condensation product of the reaction between the compouid selected froin the group consisting of conjugated cycloalkadienes 55 and halo-substituted conju.-ated cycloalkadienes and a sixmembered unsaturated heterocyclic compound - containing four carbon atoms and tvio noli-adjacent oxygen atoms in the ring. Other objects and embodiments of the invention refer- 60 rin- to alternative conjugated cycloalkadienes, halo-substitzt,d conjugated cycloalkadienes and six-membered unsaturated heterocyclic compounds containin- four carbon atoms and two non-adjaceiit oxygen atms in the ring r,5 will be referred to in the following further detailed description of the invention. It is now proposed to condense a conjugated cycloalkadiene or a halo-substituted conjugated cycloalkadiene with 2 condensation may, be used for a variety of products. For example, the condensation of hexachlorocyclopentadiene with pdioxadiene will result in a tricyclic or pentacyclic compound containing six or -twelve chlorine atoms, respectively, depending upon the molar proportion of the hexachlorocyclopentadiene to dioxadiene. Condensation of hexachlorocyclopentadione with pdioxene will result in a tricyclic compound containing six chlorine atoms. These condensations are illustrated by the following equations: c ic-cci 0 c ic CCl Ho CH + 11 1 1 0 \ HC CH ci ci 0 Hexachloro- p-dioxediene cyclopentadiene c H 0 ---I/ \ cic c C-I[ 11 ci-@-ol @ 11 ci-c C-H I - c O/ I UL 5,6,7,8,9,9-hexachloro-4a,5,8,8a-tetrabydro-5,8-methanobenzo-pdioxadiene ci-c-c-ci 0 01-0 0 ci HC OTT + 11 11 0 ]IC CH ol ol 0 ci ci I I u H 0 H c cli I -@, IC/ I - I --, -0 0 C-01 11 C)ICOI I cicoi 11 C)I-C 0 c 0-01 H 0 H ci Ul 1,2,3,4,6,7,8,9,11,11,12,12-dodecaebloro-1,4,4a, 5a,6,9,9a,10a-o,tahydro-1,4,7,O-dimetbanodibenzo-p-dioxadione ci I ci-c-c-ei 0 C H 0 ClC 8-01 Ho CH2 c ic 0 CH2 / + 11 I 1 1 cicci I I C Ho CH2 @@c CH2 ol ci 0 C H 0 @l p-dioxene 5,6,7,8,9,9-hexachloro-2,3,4a,5, 8,8a-hexabydro-5,8-raetbailobenzo-p-dioxadieiae Desirable products may also be obtained by first condensing the p-dioxene or pdioxadiene with cyclopentadiene and then reacting the product so obtained with hexachlorocyclopentadiene. These polychloro substituted polycyclic compounds are useful as inseeticides, particularly against houseflies, Mexican bean beetles, pea aphids and mites. It is also contemplated within the scope of this invention that ia conjugated cycloalkadiene containing more than one species of halosubstituents may be condensed with a six-membered unsaturated heterocyclic compound containing at least two oiygen atoms in the r:.n.a. Examples of conjugated cycloalkadienes (yr hajosubstituted conjugated cycloalkadienes which may be condensed with six membered unsaturated heterogyclic compounds containing at least two oxygen -atoms in the ring according to this invention include 1,3-cyclopentadiene a six-member unsaturated heterocyclic compound con- 70 (hereinafter referred to as cyclopentadiene), 5-chlorotaining four carbon atoms and two non-adjacent oxygen cyclopentadiene, 5,5-dichlorocyclopentadiene, 2,3-dichloatoms at an e.levated temperature. The products of this rocyclopentadione, 2,3,4-tricWororyclopentadiene, hex4-
[2]2,906-,697 chlorocyclopentadiene, 5-bromocyclopentadiene, 5,5-dibromocyclopentadiene, @,3- di@romocyclopentadiene, 2,3, 4 - tribromocyclopentadiene, hexabromocyclopentadiene, 5 -, fluorocyclopentadiene 5,5 - difluorocyclopentadiene, 2,3 - difluoroqy.'elop&ntadiene; 2,3- - trifluorogyclopentar _,4 diene, hexafluorocyclopentadiene,, 1,3 - cycl6fieiadi&ne, 1 - chloro - 1,3 !@.yclohexadiene@- 1.Z - dichloro - 1,3cyclohexadi;ene, 5,6-dichloro-1,3- Gy@lohexadiene, l-,2,3@ tnehloTo-1,3@-cycloliex@diene, 1,2,3;4-tetrachlijro1,3cyclohexadiene, 5,5,6@,6, - teirachloro - 113 -' cyclohexadiene,, octachloro -- 1,3 - cyclohexadieiie, I - bromo - 1,3c@cl8li6xadiene,.- 1,2 7 dibibm6 - I , 3 - c@clolidx-adiene,1,2,5'- tiibro'mo - 1,3 cycl'6fi6i@dieri6l l'@2,3,4 - &ii'a@ bromo - 1,3 - cyclohexadiene, octabromo - 1,3 - c@616hexadiene, 1 - fluoro - '1,3 - cycl6hexadiene, 1-,2 - difluoro-1,3-cyclohexadiene, 112,3-tr ifluoror-1,3@-cyclohexadiene, 1,2,3,4- tetraflub@o-1,3-eyelchekadiene, octafluoro-1,3-cyclohexadiene, etc. Examples of six-membered uns,@iturated heterocyclic compounds containing four caibon atoms and two n6nadjacent oxygen atoms in the ring which may be condensed with the aforementioned cycloalkadienes or halosubstitiit@d cycloalkadienes include pdioxadiene (i.e. 114--dioxin or p-dioxin),, p-dioxene (i.e. 2,3-dihydro-pdio,Kin), m-dioxene (i.e. 1,3-dioxene or m@dioxin) etc.; alkyl substitutc@dsi-,-membered unsaturated heterocyclic compounds containing four carbon atoms and two nonadjacent oxygen atoms in the ring including 2-methylp - dioxadiene, 2,3 - dimethyl - p - dioxadiene, 2,3,5,6te I tram I ethyl - p - dioxadiene, 2 - ethyl - p - dioxadiene, 3 - ethyl - p - dioxadiene, 2,3 - diethyl - dioxadiene, 2,3,4,5 - tetraethyl - p - dioxadi6ne, Z - propyl - p - dioxadiene, 2,3 - dipropyl - p - dioxadienel-: 2 - methyl - pdioxene, 2,3 - dimethyl - p - dioxen6, 2 - ethyl - p - dioxene, 2,3 - diethyl - p - dioxenc@ etc., 2 - iiiethyl mdioxin, 2 - etbyl - m - dioxin, 2,5,6 - trimethyl mdioxin, etc. I-lalo-substituted six-membered unsaturated heterocyclic c@ompo'und-s containing four carbon atow-s and two noii-adjacent oxygen atoms in the ring include 2 - chloro - p - dioxadiene, 2,3 - di6hloro - p - dioxadiene, 2,3,5,6 - tetrachloro - p - dioxadiene, 2 - bromo - p - dioxadiene, 2,3 - dibromo - p - dioxadiene, 2,3,5,6 - tetrabromo - p - dioxadiene 2 - fluoro - p - dioxadiene, 2,3difluoro - p - dioxadiene, 2,3,5,6 - tetrafluoro - p - dioxadiene, 2 - chloro - p - dioxene, 5 - chloro - p - - dioxene, 2,3 - dichloro - p - dioxene, 5,6 - dichloro - p - dioxene, 2 - bromo - p - dioxene, 2,3 - dibromo - p - diqxene, 5 - bromo - p - dioxene, 5,6 - dibromo - p - dioxene, 2-fluoro-p-diox@ne, 2,3-difluoro-p-dioxene, -5 L fl -uoro-p-di-oxene, 2-chloro-m-dioxin, 2- bromo-m-dioxifi, 2-fluoro-mdioxin, 2,5-dichloro-m-dioxin, 2,5-,6-trichloro-m-dioxin, etc. it is to be understood that the above mentioned conju-.ated cycloalkadienes, halo-substituted conjugated cycloalkadienes, six-membered unsaturated heterocyclic compounds containing four carbon atoms and two nonadjacent oxygen atoms and their halogen and alkyl,substitution products are only repre.sentative, of the classes@ of com@ounds which may be used, and that said inv@ntion is not necessarily limited thereto. The condensatioii reaction ,provided hereiri, generallycharacterized as one of the DielsAlder t I ype,, is eff6cfed at an elevated temperature in the range of from ab6ut 50' to about- 250' C. or more, and prefera@,bly at a temperature in the range of from- about 1 00' to, about 200' C. Temperatures which are greatly in excess of the upper limits are generally undesirable due to a possibility that such high tempdr I atures may cause the desired product to deteriorate. Lower temperatures are usually not used bec-ause the reaction usually takes plare too: slowly at such temperatures-. Suitable reaction pressure@s range@ from atmospheric to about 20- atmosphetes and Oven higher; superatmospberic pressum is advantageou in providing anz ess6ntially@ liquid phase-, reabtion. rhixiurez,@ said pr6ssur6 ofteii beijxg provided by charging" nitrogtii,@ gases, 4 residence time of the reactants in the reaction mixture may vary dependin-, upon the particular temperature and pressure employed, said residence time being in the range of from about 1 to about 10 hours or more. When employing temperatures in the lower portion of the hereinbefore indicated range the time required to complete the reaction wiR be relatively long, while the usd of temperatures@ iz the@ highei' portion of - the range substantiary reduces the residence time required -to c6mplete the reac10 tiorl The@ use of a temperature in the lower range and a@ shbrt- reaction tirfie will tend to- allow some unreacted starting materials to remaiii@ in the@;reaction mixture, however, these materials will not impede the recovery of the desired pi6(flict 15 The reactants wilt be present in th'e reaction mixture in a molar ratio'.@ of- Gyrloalkadiene: or polyhalocycloalkadiene to six-membered unsaturated heterocyclic compounds- containing: four. carbon atoms' and two non-adiacent@ oxygen atoms_ in the ring,@ in a: range- of@ from 0.4:1 20 ta 5,:@ 1. The use of excess of the- diene reactant, provides, an- effective diluent o.f . the reaction mix-ture thereby enabling, the,,rate of the: resultant e-,-othermic reaction- to-. be controhed within@ the desired limits. The. prpduct of the reaction @is recovered from -the reaction mixture @by. 25 frac-tional distillation or, in some cases, by c rystallization., The utireacted starting materials being tfie lowest boilin-g. coiilpon6nt@ of the reaction mixtur6 may be rem6ved therefrom meiely by distilling the saine frorn the mixture, leaving a resildue comprising the desired con30 deksation products. The latter res-idue ma be thereafter puriffed@, for example, by ffactional distiuation" crystallization, extraction or by other means well-kndwn iii fhe ari@ pr utilized directly without further treatment for t@e p,r'eparation of other @ompositions. If the reac35 tibn pr'od-uct' is to be used as an insdcticide the product may I b6 additionally tieated- if so desired, to introduce addiiibii'@l'.halogen substiiiients into th@ structiire. rii addition tYe condensati-on prod'uct may al'so be treated in ottier )@ays, for exam@le, by reactibn' *ith m- etal@ to' 40 effect total or partial dehalogenation or with alk@lifie ni@Lteri@l tlo 6ff6ct total or pariial deh@diohalogenation. lt'is, als6 conteinplat'ed'withiii the sd6pe of thi@ iiiv6iitioii t'h@t the cdiid'en'sation pfote@s described: h&rei'n-'ma'y-. be. 4iffe6t6d in the ttd@eiice of an inert sol@eiif of diluen-t 45 which-'willn-otb6re@cfive'at'theteiriperatures--ased. Tli6, preferred diluents which may be used in@lude ali@hatic and aromatic hydrocarbori l alcohon ' eth@rs, 6t6., iu@@ a5 he-xpne', hept toluen i e, xyl@ , ane, bbnz'en'e, ne@, eftl alcbholl ethyl ether, etc. rao The physical prbp@@,rCie of the preseni @ory@yclic@on,'densatfo-.1@ prod'ucts and the effects the@ h@LVe on entomologfcal -'LoiTqs o't life meiltb them particularly desi@able a@ insecticidfes@ and iifsect repellants, the compouiid@ havfng' niariy of the features desired of materials for this purr pos,. They are, for example, toxic to insect@ Nvfiich are @5 dlest'tuct;.ve- of plant life and materiats@ xiorrnally stibje@t to insecf infestation, their toxic eff.-cts being riaiiifest@d' by contact of the poisoiy with the inseet. The iT@5ecti@id'es compri@ing the presenf compolind are thus effective agains 't chewiiag' ,@ven@ as- suckiiig tyl_)es of insects Voratility, Go whi h isas c art rrioortani characteristic of iinsecticides is usualfy de-pendent upon the mol'ecular weight of the com'-pound. The compounds of the present invention ard @ufficieiitly @olatile, so that@ when applied to plaiif life iiitended for subsequent htiman consumption, the plants 65 when harvested and after allowing a reasonable time f6r evaporation of the applied insecticide therefrohl retiiri none of the toxitant to preventuse of the plant for cortsumption a food. Oji the other hand, the compound@, 70 are of sufficiently limited volatility due to their relatively hi,@h molecular weiahts to be retained on the substance for tnd tim6 requiredi ta accomplish the toxic effects 6f the conipothdsi In additiori, the volatilit@ afid@ ret6ntive, r-apacit-y of the compolind's may be varied'at@ will by' carbouldioxid6ior,otlie,rinert: - -into the@reactorThe. 7r, combim'lig them kvith suktabl--'fixing ae,@ntsz,,vhich, rediiee
[3]2igO5,697 or @romote their volatilization, as desired. Thus, the compounds may be dissolved in a suitable high boiling scilvent, such as a mineral @:)r vegetable oil, petroleum, etc.; a wax, such as paraffin wax, beeswax, etc.; a high molecular weight alcohol or ether such as myricyl al- 5 cohol, dibutyl ether, etc.; or they may be emulsified with water by the addition of Ln emulsifying agent, such as a surface actiie agent, to the mixture of components. T'he latter solvents and dispersants may also be employed for the specific purpose of reducing the concentration of 30 insecticide to the desired level in a specific insecticide fon-nulation. The particular formtilation of active components in combination with the solvent or dispersant will depend upon its application. Compositions containing as high as 20% of active component may be preferred, in 15 some instances where deep penetration of the insecticide is desired, as in the treatment of fibrous material, such as wood, for extinction of a particular infestation, for example, wood termites. For other purposes the required concentration of active components in the formulation 2 0 may be as low as 0. 1 %, as for example, in the treatment of fabrics for destroying moth larvae. In utilizing the present irsecticidal compolinds against most insects, a composition containing from about 0.1% to about 5% by weight of the active component is highly effective. The 25 choice of the most desirable solvent or dispersant further depends upon the method utilized to apply the insecticidal composition to the infested article. For example, a low molecular wei,-ht, normally gaseous carrying agent for the active insecticidal component, such as propane, butane, 30 the Freons, etc., may be compressed and liquefied into a small bomb containing the insecticide. Upon release of pressure from the bomb, the liquefied carrier vaporizes and suspends a quantity of the active component therein, thus providin@ a convenient spraying method of applying 35 the insecticide. The active component may also be dissolved in a liqu;d carrier, such as kerosene, an alcohol, ester, ketone, etc., and the resulting solution atomized by a suitable spraying device. The process of the present invention wherein a con40 jugated cycloalkadiene or halo substitlited conjugated eycloalkadiene and a six-membered unsaturated heterocyclic compound containing four carbon atoms and two non-adjac,-nt oxy.-en atoms in the ri@ig are condensed, may be effected in any suitable manner and may com45 prise either a batch or a continuous type operation. For example, when a batch typ-- operation is used, a quantity of the reactants, namely, the cycloalkadiene or halosubstituted cycloalkadiene and the six-membered heterocyclic compound containing four carbon atoms Pnd two 50 non-adjacent oxygen atoms in the ring, with or without a diluent, are placed in an appropriate condensation apparatus containing mixing and heating means. The reaction vessel is heated to the desired temperature and maintained at such temp-@rature for a predetermined pe.-iod Of C,5 time, usually not over 10 hours. At the end of this time, the reaction vessel and contents thereof are cooled to room temperature and the condensation product is separated by conventional means such as fractional distillation, crystallization, extraction or other means well- 60 known in the art. The condensation products of this invention may also be prepared by a continuous process wherein the reactants are continuously charged to a reaction vessel maintained at suitable operating conditions of temperature and 65 pressiire. The condensation product stream is continuously withdrawn from the reactor and separated from unreacted starting materials and/or unwanted side reaction products which may have formed, and purified by conventional means hereinbefore set forth, while the un- 70 reacted compounds are recycled for further use as a portion of the feed material. Examples of condensation products prepared according to this invention include 4a,5,8 ,8a-tetrahydro-5,8- methanobenzo-p-dioxadiene, 2,3,4a,5, 8,8a-hexahydro-5,8- 75 6 methanobenzo-p-dioxadiene, 5,6,7,8,9,9-hexachloro - 4a,5, 8,8a-tetrahydro-5,8- methanobenzo - p - dioxadiene, 5,6,7, 8,9,9-hexachloro - 2,3,4a,5,8,8a -,hexahydro-5,8- methanobenzo - p - dioxadiene, 6,7-dichloro - 2,3,4 a,5,8,8a-hexahydro - 5,8 - methanobenzo - p - dioxadiene, 6 7-dichloro4a,5,8,8a - tetrahydro - 5,8 - methanobenzop"@ioxadiene, 2 - mefnyl - 5,6,7,8,9,9 - hexachloro - 2,3,4a,5,8,ga-hexahydro - 5,8 - methanobenzo - p - dioxadiene, 2-methyl5,6,7,8,9,9 - hexachloro - 4a,5,8,8a-tetrahydro - 5,8,-methanobenzo - p - dioxadiene., 2,3-dimethyl-5 ,6,7,8,9,9-hexachloro - 2,3,4a,5,8,8a - hexa@fiydro - 5,8-methanobenzo-pdioxadiene, 2,3 - dimethyl - 5,6,7,8,9,9 - hexachloro4a,5, 8,8a - tetrahydro - 5,8-methanobenzo - p - dioxadiene, 2ethyl - 5,6,7,8,9,9 - hexachloro - 2,3,4a,5,8,8a - hexahydro - 5,8 - meth anobenzo-p-dioxadiene, 2-ethyl5,6,7,8,9 ' 9 - hexachloro - 4a,5,8,8a - tetrahydro - 5,8 - methanobenzo - p - dioxadiene, 2,3 - diethyl - 5,6,7,8,9,9,-hexachloro - 2,3,4a,5,8,8a - hexal-iydro - 5,8 - methanobenzop - dioxadiene, 2,3 - diethyl - 5,6,7,8,9,9 - hexachloro - 4a, 5,8,8a - tetrahydro - 5,8 - methanobenzo - p - dioxadiene, 2,5,6,7,8,9,9 - heptachloro - 2,3,4a,5,8,8a - hexahydro 5,8 - methano - 1 4 - benzo - p - dioxadiene, 2,5,6,7,8 ,9,9,heptachloro - 4a,@,8,8a - tetrahydro - 5,8 - methanobenzop-dioxadiene, 2,3,5,6,7,8,9,9 - octachloro - 2,3,4a,5,8,8ahexahydro - 5,8 - methanobenzo - p - dioxadiene, 2,3,5, 6,7,8,9,9 - octachloro - 4a,5,8,8a - tetrahydromethanobenzo - p - dioxadiene, 1,2,3,4,6,7,8,9,11,11,12,12-dodecachloro - 1,4,4a,5a,6,9,9a,10a - octahydro - 1,4,6,9- diTnethanodibenzo-p-dioxadiene, 1,4,4a,5a,6,9,9a,10 a-octahydt-o1,4,6,9- dimethanodibenzo-p-dioxadiene, etc. The present invention is further illustrated with respect to specific embodiments thereof in the following examples which, however, are not intended to limit the generally broad scope of the present invention in strict :accordance therewith. Example I Equirnolar proportions of bexachlorocyclopentadiene and p-dioxene (i.e., 2,3-dihydro-pdioxin) are placed in a reaction vessel. The vessel is slowly heated to a temperature of approximately 145' and maintained thereat for a period of approximately four hours, the contents of said vessel being continiliously stirred during this period. At the end of this time the vessel iand contents thereof are allowed to coal to room temperature and the reaction products therein are subjected to fractional distillation under reduced pressure. The fraction comprising 5,6,7,8,9,9 - hexachloro - 2,3,4a,5,8,8a - hexahydro - 4,8methanobenzo-p-dioxadielie is separated therefrom. Example II Equimolar proportions of cyclopentadiene and p-dioxene are placed in a reaction vessel which is heated to a temperature of approximately 180'. The contents of the vess@l are subjected to continuous mixing while said vessel ismaintained at the abovementioned temperature for a period of about five hours. Atthe end of this Ume the vessel and contents thereof are allowed to cool to room temperature. The reaction product is then subjected to fractional distillation under reduced pressure and the cut, comprising 2,3,4a,5,8,8a-hexahydro-5,8methanobenzo-p-dioxadiene, is separated therefrom. Example III Two molecular proportions of hexachlorocyclopentadiene and one molecular p@roportion of p-dioxadiene are placed in a reaction vessel similar to @that described in the above examples. The vessel is heated to a temperature of -about 120-130' and maintained thereat for a period of about ten hours, the contents of said vessel being continuously stirred during this residence time. At the end of this period the vessel and contents thereof are cooled to room temperature and the Teaction product subjected to fractional distillation under reduced pressure. T@he cut, comprising 1,2,3,4,6,7,8,9,11,11,12,12-dodec4-
