US2802012A

US2802012A - Polycyclic insecticidal compounds

Info

Publication number: US2802012A
Application number: US501455A
Authority: US
Inventors: Jerome G Kuderna
Original assignee: Shell Development Co
Current assignee: Shell Development Co
Priority date: 1955-04-14
Filing date: 1955-04-14
Publication date: 1957-08-06
Anticipated expiration: 1974-08-06
Also published as: FR1149521A; GB789113A; DE1137256B

Description

United States Patent 2,802,012 POLYCYCLIC INSECTICIDAL COMPOUNDS Jerome G. Kudema, Denver, Colo., assignor to Shelli Development Company, New York, N. Y., a corporation of Delaware No Drawing. Application April 14, 1955, Serial No. 501,455

21 Claims. (Cl. 260-310) This invention pertains to novel chemical compounds and to a method for their preparation. More particularly, the present invention pertains to certain novel nitrogen-heterocyclic compounds and to a method for their preparation. In another of its important aspects the invention pertains to the use of these novel compounds to aid in the control and eradication of insects and similar pests and to new pesticidal compositions suitable for this purpose.

The compounds to which the invention pertains may be referred to and defined as nitrogen-bridged tricyclo- [5.2.1.0 8 decenes wherein nitrogen bridge links the carbon atoms in the Nos. 3 and 5 positions of the tricyclodecene structure. and is composed solely of two directly interconnected nitrogen atoms. According to one of the aspects of the invention the said two nitrogen atoms are interconnected by an unsaturated linkage and the nitrogen bridge, therefore, is an azo or N=N bridge. In accordance with another aspectof the invention, the said two nitrogen atoms are interconnected by a single (saturated) linkage, and the nitrogen bridge, therefore, is a hydrazo, biimino, or

bridge whereon the exocyclic valences of the nitrogen atoms are satisfied by attachment by hydrogen, alkyl, acyl, carbalkoxy, epoxy, carbonyl or other substituent.

The chemical name tricyc1o[5.2.1.0 8 decene refers, in accordance with the Baeyer plan of nomenclature (The Ring Index. Ring Systems Used in Organic Chemistry, by Patterson and Capell. Reinholt. 1940), to the structure that is represented by the following formula present new products thus can be represents by the formula liijiijl Where the two nitrogen atoms are interconnected by a double bond, the novel compounds of the invention can be referred to and defined as 4,5 diazatetracyclo- [6211 10 4,9 dodecadienes. Where the two nitrogen atoms are interconnected by a single (saturated) bond, the novel compounds of the invention can be referred to and defined as 4,5-diazatetracyclo[6.2.1.1 0 ]-9-dodecenes. In both cases the position numbers are assigned as indicated in the following structural for- With regard to this, as well as the preceding structural formulas, it will be understood that only the atoms essential to the novel cyclic structure have been depicted, and that in each case the depicted atoms will be bonded to a suificient number of exocyclic atoms or groups of atoms to satisfy any remaining valences of the nuclear atom in question. i i

It has been discovered that compounds containing the foregoing nitrogen bridged tricyclo[5.2.1.0 8 decene structures can be prepared by causing certain derivatives of azodicarboxylic acid, especially esters, amides,

or amidines thereof, to react by 1,4-addition with a con jugated cyclopentadiene hydrocarbon and then reacting the resulting intermediate reaction product by a second 1,4-addition with a second molecule of a cyclopentadienoic compound to produce the nitrogen-bridged tricycledecene structure. The immediate product of these two successive 1,4-addition reactions is a nitrogen-bridged tricyclo[5.2.1.0 ]-8-decene wherein the two nitrogens of the nitrogen bridge are substituted by formic ester, carboxamido, or carboxamidino (or carboxamidino salt) groups according to the identity of the azodicarboxylic acid derivative used as starting material. These nitrogenbridged tricyclo[5.2.1.0 8 decenes wherein the nitrogens are substituted by an exocyclic group can be converted by decarbalkoxylation, decarboxamidation, or decarboxamidination to corresponding derivatives wherein the exocyclic bond of at least gens is satisfied by hydrogen. The products wherein both of such exocyclic bonds are linked to hydrogen undergo oxidation readily to yield valuable nitrogen-bridgen tricyclo [5.210 8 decenes wherein the bridge nitrogens are interconnected by a double bond, that is to say, 4,5 diazatetracyclo[6.2.11 .0 4,9 dodecadienes.

In terms of chemical equations (wherein only the essential atoms or groups are shown and wherein R represents a formic ester group,

one of the two nuclear nitroa carboxamido group, a carbox- 13 Derivatives of azodicarboxylic acid which can be employed as starting materials for the preparation of the novel products of this invention include the esters, amides, and amidines thereof. The ester may be aromatic, aliphatic or cycloaliphatic, i. e., a dialkyl azodicarbcxylate, a diaryl azodicarboxylate, or a cycloalkyl azodicarboxylate, or a mixed ester, including, without being limited to, dimethyl azodicarboxylate, diethyl azodicarboxylate, dibutyl azodicarboxylate, dihexyl azodicarboxylate, d1- octyl azodicarboxylate and the homologous and analogous dialkyl azodicarboxylates, diphenyl azodicarboxylate, ditolyl azodicarboxylate, dinaphthyl azodicarboxylate, and esters of other unsubstituted as well as substituted monocyclic and polycyclic phenols, and esters of alicyclic alcohols such as dicyclohexyl azodicarboxylate, dicyclopentyl azodicarboxylate, and bis-trirnethylcyclohexyl azodicarboxylate. Amides of azodicarboxylic acid which can be employed include azoformamide as Well as N-substituted derivatives thereof, such as N,N'-dialkylazoforma'rnides. The corresponding aniidines derived from azodicarboxylic acid may also be employed, such as azodicarboxylic diamidine,

and its alkyl substitution products. In general, the pre ferred starting materials are the aliphatic esters of a20- dicarboxylic acid, especially the esters of alcohols containing from one to about six carbon atoms.

As the cyclopentadiene hydrocarbon reactant there preferably is employed 1,3cyclopentadiene itself. Lower alkyl substitution products of cyclopentadiene may be employed, however, such as the methyl-1,3-cyclopentadienes, the ethyl-1,3-cyclopentadienes, the dimethyl-1,3- cyclopentadienes, the butyl-1,3-cyclopentadienes, and related conjugated cyclopentadienes containing one or more alkyl substituents of from one to four carbon atoms.

The cyclopentadienoic compounds with Which'the addition product of the cyclopentadiene hydrocarbon and azodicarboxylic ester, amide, amidine or amidine salt is caused to react by a 1,4-addition reaction, vmay have substituted on the conjugated cyclopentadiene ring, one or more substituent groups or atoms, such as alkoxy, nitro, cyano, acyloxy, formyl, acyl, ca-rbalkoxy,carboxyl and/ or halogen, especially bromine, chlorine, and fluorine.

As the cyclopentadienoic compound there preferably is employed a conjugated cyclopentadiene hydrocarbon that is, substituted on the ring by one or more atoms of halogen, preferably bromine or chlorine. Especially preferred are the halogen-substituted cyclopentadiene hydrocarbons containing at least four atoms of halogen directly substituted on the conjugated ring. Representative of this preferred class are such halogen-substituted cyclopentadiene hydrocarbons as hexachloro-1,3-cyclopentadiene, hexabromo 1,3 cyclopentadiene, 1,2,3,4 tetrachloro 1,3 cyclopentadiene, 1,2,3,4,5 pentachloro- 1,3 cyclopentadiene, l,2,3,4 tetrabromo 1,3 cyclopentadiene, and their analogs containing from four to six atoms of halogen substituted on the conjugated five-membered ring. The halogens preferably may be the only substituents on the cyclopentadienoic ring, or one or more additional substituents may be present. Substituents, other than halogen, which may be present include in particular relatively non-polar group, such as alkyl groups and alkoxy groups. Substituted cyclopentadienoic compounds containing such relatively non-polar groups and suited to the invention include the halogenand alkyl-substituted conjugated cyclopentadienes, such as 5- methyl 1,2,3,4 tetrachloro 1,3 cyclopentadiene, 1 methyl 2,3,4,5,5 pentachloro 1,3 cyclopentadiene, 1 methylpentachloro 1,3 cyclopentadiene, 5- methylpentachloro 1,3 cyclopentadiene, 5,5 dimethyltetrachloro 1,3 cyclopentadiene, and 1,4 dimethyltetrachloro 1,3 cyclopentadiene, as well as the alkoxyand halogen-substituted conjugated cyclopentadienes, such as 5,5 dimethoxytetrachloro 1,3 cyclopentadiene, 5,5 diethoxytetrachloro 1,3 cyclopentadiene, 5,5 dimethoxytetrabromo 1,3 cyclopentadiene, and 5,5 dimethoxydibromcdichloro-1,3-cyclopentadiene.

The reaction between the conjugated cyclopentadiene hydrocarbon and the ester, amide, or amidine of azo'dicarboxylic acid to produce the intermediate N-substituted 2,3-diazabicyclo-[ 2.2911-5-alkene may be carried out by mixing the two reagents, in solution if desired, and allowing the mixture to stand preferably at room temperatures or below to effect the desired 1,4-raddition reaction. Temperatures between aboutt) C. and about 25 C. preferably are employed. The two reactants may be employed in about equimolar amounts, although an excess of either reactant may be employed without departure from the invention. As solvents there may be employed such inert media as benzene, dioxane, diethyl ether, heptane, and the like, or such relatively polar organic solvents as methanol, ethanol, isopropyl alcohol, chloroform, glacial acetic acid, and glacial formic acid. The time required for completion of the reaction Will depend upon the reaction temperature as Well as upon the identity of the reactants; in general, reaction times not over about 48 hours will suffice. After completion of the reaction, the N-substituted 2,3-diazabicyclol2.2.1]-5-alkene may be recovered from the reaction mixture by such conventional methods as distillation, crystallization, or extraction with selective solvents, or the crude reaction product may be utilized Without purification for the succeeding re action with the polar-substituted cyclopentadiene compound.

The reaction of the N-substituted 2,3-diazabicyclo- [2.2. l]5-.al'kene with the substituted conjugated cyclo-.

pentadiene compound to produce a 4,5-diazatetracyclo- 6.2.1.l .0 ]-9-dodecene takes place upon heating the N-substituted 2,3-diazabicyclo[ 2.2.1]-5-alkene and the substituted cyclopentadiene compound together at elevated reaction temperatures above about 50 C. The reaction temperature should be high enough to lead to a practicable rate of reaction, but not so high that loss of product would be incurred by decomposition either of the reactants or the reaction product. In general, reaction temperatures between about 50 C. and about 200 C. are prefer-red, an especially preferred range being from about C. to about C. The reaction can be caused to occur with either the N-substituted 2,3-diazabicyclo- [-2.2.1]-5-alkene or the substituted cyclopentadiene reactant in excess, or with equirnolar amounts of the two reactants; The yield of addition product, however, is influenced .by the mole ratio between the reactants. For maximum yields the presence of an excess of the substituted cyclopen-tadiene reactant is desirable. With a two-fold molar excess of the. substituted cyclopentadiene reactant higher yields generally are obtained than when the reactants are employed in equimolar amounts, and even higher yields generally are obtained when the mole ratio is in the order of 5:1. For optimum yields of the 4,5-diazabicyclo[6211 ]-9-dodecene, the substituted cyclopent-adiene reactant and the N-substituted 2,3- diazabicycl o[t2.2.lJ-S-alkene preferably are employed in mole ratios within the range of from about 2:1 to about 10: 1, although it will be understood that both higher and lower ratios are operable.

The reaction between the N-substituted 2,3-diaza-bicyclo[2.2 1]-5-allcene and the substituted conjugated cyclopentadiene ordinarily will be carried out in a closed system, such as an autoclave, since excessive losses through volatilization otherwise would be likely to be incurred. In appropriate cases, the reaction may be carried out by refluxing the two reactants together, with or without an inert diluent or solvent, or even by heating the mixture at temperatures below the boiling point in open equipment.

In order to reduce or prevent loss of the substituted cyclopentadiene reactant through autopolyme-rizat-ion it is desirable to include a small amount of any of the various known polymerization inhibitors in the reaction mixture, such as hydroquinone, methylene blue, resorcinol, p-tbutylhydroquinone, or the like. The polymerization inhibitors suitably may be added in amounts between about 0.001 and about 10% by weight of the reaction mixture, although these limits are not critical. Where the substituted cyclopentadiene reactant contains halogen substituents, small amounts of hydrogen vhalide may be evolved spontaneously under the reaction condition. In order to minimize or prevent side reactions iikely to be brought about by the catalytic efiects of this liberated acid, it is desirable to include in the reaction mixture a small amount of .an acid-scavenger, for example, an oxirane compound such as styrene oxide, epichlorohydrin, a glycidyl ether, or an alkene oxide, which will combine with and form innocuous products from the liberated hydrogen halide. In general, addition of between about 1% and about 20% of the acid-scavenger, based upon the weight of the reaction mixture will serve adequately to neutralize such liberated acid. p

The 4,5-diazatetracyclo[6.2.11 .0 ]-9-dodecene that is produced by the reaction of the substituted conjugated cyclopentadiene and the N-substituted 2,3-diazabicyclo- [=2.2.1]-5-alkene will contain on the ring nitrogen atoms substituents that correspond to the N-substituents present in the 'N-substituted 2,3-diazabicyclo[2.2.1]-5alkene, e. g., carbalkoxy, carboxamido, carboxamidino, or carboxamidinates and additionally on ring carbons thereof, the polar substituen-t or substituents that correspond to the substituent or substituents present on the ring of the substituted conjugated cyclopentadiene reactant. For example, where the substituted cycl-opentadiene compound used is hexachlorocyclopentadiene and the N-substituted 2,3-diazabicyclo[2.2.l]-5a-lkene is 2,3-dica-rbobutoxy- 2,3-diazabicyclo[ 2.2.1l-5aheptene, the product will be 4,5 dicarbobutoxy 1,8,9,10,ll,l1 hexachloro 4,5 diazatetracyclo[6.2.1.1 .0 ]-9-dodecene, having the plawhile if the substituted cyclopent-adiene compound is 5 ,5 dimethoxytetrachloroal,3 cyclopentadiene and the N-substituted 2,3- diazabicyclo[ 2.2.1]-5-alkene reactant is 2,3-

diazabicyclo [1242. l -5-heptene-2,3 dicarbox'amidine the product will be 1, 8,9,10-tetrachloro l1,l1-dimethoxy4,5- diazatetracyclo 6. 2:1 1 0 -9-dodecene-4,5 dicarboxamidine having the planar formula The N-substituted 4,5'diazatetracyclo[ 6.2.1.1 .0 9-dodecenes thus obtained in accordance with the invention can "be converted to the corresponding novel hydrazo compounds by replacing the substituents on the nuclear ring nitrogen atoms by hydrogen atoms through decarballcoxyla-tion, deoarboxarnidation, or decarboxamidination, as the case may be, or they may be converted to corresponding novel azo compounds by successively replacing the N-substituents by hydrogen and oxidizing the resulting hydrazo compound to the azo derivative.

Substitution of hydrogen for the formic ester, carbox- .amido, or carbox-amidino groups substituted on the nuclear nitrogens of the novel Nasubstituted 4,5-diazatetracyclo[6.2.1.1 0 ]-9-dodecenes may be effected by heating the :N-substituted 4,5-diazatetracyclo[6.2.1.1 0 l-9-dodecenes in the presence of a decarb'allcoxylation, deca-rboxamidat-ion, or decarboxamidination agent, such as a strong alkali or a strong .acid. The reactions can be so controlled as to produce products resulting from replacement of only one of the two nitrogen substituents by hydrogen, or both of the two groups can be replaced by hydrogen. For removal of the formic ester groups by deca-rballcoxylation, the preferred agents are strong bases, such as alcoholic solutions of alkali metal alkoxides, alcoholic potassium hydroxide, alcoholic lithium hydroxide, alcoholic solutions of quaternary ammonium bases, or the like. Acid decarbalkoxylation agents which may be employed include strong acids, such as concentrated hydrochloric acid, sulfuric acid, phosphoric acid, ethanolic HCI, trichloroacetic acid, etc. Where the decarbalkoxyl'ation is carried out in alkaline media the free hydrazo base is formed. The hydrazo basesof the invention, when in the free state, are readily oxidized even upon expo-sure to the atmosphere to yield the corresponding azo compounds, or 4,5-diazatetracyclo[6.2.1.l .0 ]-4,9-do-. decadienes and, therefore, where it is desired to retain the hydrazo base as such, care must be taken to avoid excessive exposure to the atmosphere. The hydrazo bases can be stabilized by conversion to a mineral acid salt, such as the hydrochloride, sulfate, phosphate, nitrate or the like, or to a salt of an organic acid, such as the formate or acetate, conveniently by neutralizing the base in solution in an organic medium, such as ether or benzene, by reaction with an excess of the acid. Where the decarbalkoxylation is carried out in acid media the hydrazo salt is formed directly and may be recovered as such.

The "decarbalkoxylation of the novel N carballcoxy-4,5 diazatetracyclo[621.1 .0 ]-9-dodecenes of the inven tion can be carried out at room temperatures or it can be accelerated by the application of heat to the reaction mixture, e. g., by conducting it at steam bath or even higher temperatures. Recovery of the product may be accomplished by conventional procedures, such as by distillation, crystallization, or extraction with selective solvents.

Decarboxamidation and decarboxamidination of the N carboxamidoand N-carbox-amidino-4,5-diazatetracyclo- [6.2.1.1 i0 ]-9-dodecenes of the invention may be accomplished by heating the N-substituted compound with water preferably in the presence of a small amount of mineral acid or :an alkali as catalyst.

The novel heterocyclic hydrazo compounds of the invention, that is to say, the 4,5-diazatetracyclo ['6.2.'1.1 0 ]-'9dodecenes, are useful chemical intermediates for the preparation of other derivatives than the azo deriva tives, or 4,5-diaz-atetracyclol6.2.11 .0 ]-4,9-dodecadienes. For example, they may be reconverted, where desired, to the N-carba-llcoxy-4,5-diazatetracyclo[6.2.1. 1 .0 l-9-dodecene-s by reaction with alkyl chloroformates. Instead of preparing the N-carboxamido-4,5- diazatet-racycl-o[-6.t2.1.1 .0 ]-9-dodecenes of the invention by 1,4-addition of an N-carboxamid-o-2,3-diazabicyclo[2. 2.1]-5aalkene with a conjugated cyclopentadiene compound having [one or more electron-attracting substituent-s on the ring, they may be prepared by reaction of the corresponding N carbalk oxy 4,5 diazatetracyclo- [6.2.1.1 .0 -9-dodecenes with ammonia or primary or secondary amines. The nitrogen-unsubstituted hydrazocompounds of the invention can also be employed as intermediates for the preparation of N-acyl-4,5-diazatetracyclo["6.2.1.1 .0 ]-9-dodecenes by reaction with acid halides or acid anhydrides, for example, 4-acetyl-l,8,9,- 10,11,11 hexachloro-4,5-diazatetracyclo{6.2.1.l- .0 ]-9- dodecene and 4,5-dipropionyl-1,8,9,10,l1,11-hexachloro- 4,5 diazatetracyclo'[6.2.1.1 .0 9 dodecene; of 4 or 4,5 alkyl-4,S-diazatetracyclo[6.2.l.1 .0 -"]-9-dodecenes by reaction with alkyl iodides, for example, 4,5-dimethyl- 1, 8,9,l0,11,1l-hexachloro-4,5 di-azatetracyclo[6.2.1.1. ]-9-dodecene, 4,5-diethyl 1,'8,9,10,l 1,1 l-hexachloro- 4,5-diazatetracyclo[6211 0 ]-9 dodecene, and 4- ethyl- 1,8,9,10,1 1,1 1-hexachloro-4,S-diazatetracyclo [6.2.1 l .0 ]-9-dodecene; of corresponding N-nitroso-'4,5-diaz-atet-racyclo[6.2.l.1 .0 l-9-dodecenes by reaction with nitrosyl halides, such as 4-nitroso-l, 8,-9,l0,l1,11-hex-achloro-4,5-diazatetracyclo[6.2.l.1 .0 ]9-dodecene; 0f N a-ryl and N,'N-diaryl derivatives, such as 1,-8,9,10,11,l1- hexachloro- 4-phenyl-4,5-diazatetracyclo [6.2.l.1 .0 -9- dodecene and 4,5-di-p-nitrophenyld,8,9,l0,l1,11-hexachloro-4,5-diazatetracyclo [6.2.1.l .0 -9-d-odecene; and of monoand di-ni tramine derivatives, such as 1,89,10,- 11,l1 hexachl-oro-4-nitro 4,5-diaz'atetracyclo[6.2.1.1 0 l-9-dodecene. The azo compounds of the invention can be converted to highly toxic azoxy derivatives, such as 1,*8,9,10,11,11 hexachloro-4,5-d-iazotetracyclo[6.2.1. 1 .0 ]-4,9dodec-adiene-4 oxide, by peroxidation with peracids such as perbenzoic acid, peracetic acid, persuccinic acid, etc.

The following examples illustrate certain of the specific embodiments of the novel compounds of this invention. It will be understood that the examples are presented with the intent of illustrating the invention and that they do not limit the scope thereof as it is defined by the appended claims.

EXAMPLE I Preparation of 4,5-dicarbeth0xy-1 ,8,9,10,1 I ,11 -hexach'l0- r0-4,5-diazatetracyclo[6.2.11 .0 -9-dodec-ene Diethyl azodicarboxylate, prepared by oxidation of the product formed from hydrazine hydrate and ethyl chloroformate by known methods, was mixed with an equimolar amount of cyclopentadiene in ether solution and the mixture was allowed to stand at about 15 C. for about 16 hours. The addition product, diethyl 2,3-diazabicyclo- [2.2.1]--heptene-2,3-dicarboxylate, was recovered by distillation of the resulting mixture, B. P. l05-113 C. under 0.1-0.3 millimeter mercury pressure. Yield, 97%. Twenty-four grams (0.1 mole) of the adduct and 27.3 grams (0.1 mole) of he'xachlorocyclopentadiene then were sealed in a glass pressure-resistant vessel and the mixture was heated in an-oil bath at 115 C. for 20 hours. Distillation of the resulting mixture in vacuo led to the recovery of 13 grams of unreacted hexachlorocyclopentadiene and of 7 grams of unreacted diethyl 2,3-diazabicyclo[2.2.1]- 5-heptene-2,3-dicarboxylate. The residue remaining in the still kettle was repeatedly extracted with heptane and the combined extracts were evaporated to leave a dark viscous oil. Solution of the oil in methanol followed by precipitation by dilution with water and recrystallization from aqueous methanol yielded 22.5 grams of crystalline product, M. P. 107-110" C. This *product was aseaoia recrystallized from a mixture of methanol and aqueous ammonia to yield the purified 4,5-dicarbethoxy- 1,8,9,10,11,11- hexachlorotetracyclo- 4,5- diazatetracyclo [621.1 .0 ]-9-dodecene as white crystals melting at 1l0-111 C. Analyses: found, 37.5% C, 3.12% H, 41.7% Cl; calculated for C16H16CleN204, 37.4% C, 3.12% H, 41.5% C1. The structure of this product can be represented by the following planar formula:

The product can also be identified by the chemical name 2,3-dicarbethoxy-5,6,7,8,9,9- hexachloro-l,2,3,4,4a,5,'8,8aoctahydro-1,4,5,8-dimethanophthalazine.

In other experiments, yields of the same product better than of theory were obtained by employing the hexachlorocyclopentadiene in amounts corresponding to from 2 to 5 moles per mole of the 2,3-dicarbethoxy-2,3-diazabicyclo[2.2.11-5-h6ptene.

EXAMPLE II 4,5-dicarb0niethoxy-1 ,8,9,10,1 1 ,1 I -hexachloro-4,5- diazatetracyclo [6.2 .1 .1 .0 -9-dodecene 2,3-dicarbomethoxy-2,3- diazabicyclo[2.2.1]-5- heptene was prepared by reacting cyclopentadiene and dimethyl azodicarboxylate in approximately 2:1 mole ratio at about 5 for one hour. The product was recrystallized from methanol, M. P. 81.5-82.5 Yield 90%. To a mixture of 23.3 grams (0.11 mole) of the 2,3-dicarbomethoxy- 2,3-diazabicyclo[2.2.l1-5-heptene and 30 grams (0.11 mole) of hexachlorocyclopentadiene there was added about 0.1 gram of p-t-butylhydroquinone as polymerization inhibitor and about 2.4 grams of styrene oxide as an HCl-scavenger. The resulting mixture was heated over a period of two hour to C. and held at this temperature for 4.5 hours. After standing overnight at room temperature the mixture again was heated to 135 C. and held at this temperature for an additional 3.5 hours. The mixture then was extracted with hexane and the extract was concentrated to yield 4,5-dicarbomethoxy 1,8,9,10,11,l1- hexachloro- 4,5- diazatetracyclo- [6.2.l.1 .0 ]-9-dodecene as a solid product which after recrystallization from isopropyl alcohol melted at 143-44 C. This structure of this product can be presented as follows:

Melting point of recrystallized product, 144.8145 C.

A mixed melting point with the product of the first experiment described in this example showed no depression of melting point. Analyses: found, 43.6% C1, alkoxyl equivalent 242; calculated, 43.9% C1, alkoxyl equivalent 242.5.

EXAMPLE III 4,5 dicarbobutoxy 1,8,9,10,11,11 hexachloro 4,5 diazatetracycl0[6.2.1.1 0 9 dodecene Dibutyl azodicarboxylate, prepared by. oxidation of the product formed from butyl chloroformate and hydrazine sulfate, was reacted with cyclopentadiene at 5 C. for approximately'one hour to produce 2,3-dicarbobutoxy- 2,3-diazabicyclo[2.2.1]-5-heptene in 34% yield, boiling point ISO-52 C. under 0.7 mm. mercury pressure. To a mixture of 29.6 grams (0.1 mole) of the 2,3-dicarbbutoxy-Z,3-diazabicyclo[2.2.1]--heptene and 27.3 grams (0.1 mole) of hexachloro-1,3-cyc1opentadiene there was added about 2.4 grams of styrene oxide and a small amount of p-t-butyl hydroquinone. The resulting mixture was heated at about 135 C. for 21 hours and then cooled and extracted with acetone. The acetone was evaporated from the extract and the remaining amber liquid was purified chromatographically using alumina as the adsorbent and chloroform as the eluant. The 4,5 dicarbobutoxy 1,8,9,l0,11,11 hexachloro 4,5 diazatetracyclo[6.2.1.1 .0 9 dodecene was recovered as an amber colored viscous liquid, refractive index (1120/ D) 1.5275. Yield, 32.4%. Analyses: found, 42.6% C, 4.6% H, 37.4% C1; calculated for C20H24C16N204, 42.2% C, 4.2% H, 37.4% CI. The structure of this product can be represented by the following planar formula:

$1 ll 15. An alternative name for the product is 2,3 dicarbobutoxy 5,6,7,8,9,9 hexachloro 1,2,3,4,4a,5,8,8a octahydro l,4,5,8 dimethanophthalazine.

EXAMPLE IV 1,8,9,10,11,11 hexachloro 4,5 diazatetracyclo- [621.1 .0 1 9 dodocene hydrochloride This example illustrates a typical procedure for decarbalkoxylation of products of the type illustrated in the three preceding examples. In this experiment, 6 grams (0:012 mole) of the product described in Example I was suspended in a solution prepared by dissolving 2.8 grams of 85% KOH in 30 milliliters of absolute methanol. The mixture was warmed on a steam bath for a few minutes, cooled, allowed to stand overnight. The separated potassium carbonate was filtered and washed with methanol and the combined washings and filtrate were evaporated to dryness. The residual solid was extracted with diethyl ether and the extract was acidified with dilute aqueous HCl to precipitate the hydrazo salt. Recrystallization from methanol yielded the purified feathery needles subliming at about 300 C. Yield, 85%. Analyses: found, 9.1% titratable (Volhard) Cl, neutralization equivalent 395; calculated, 8.8% titratable Cl, neutralization equivalent 405. The structure of this product can be represented by the following planar formula:

In another experiment, the decarbalkoxylation was carried out by heating 4,5- dicarbethoxy 1,8,9,10,l1,11 hexachloro 4,5 diazatetracyclo[6.2.l.1 .0 9 dodecene with concentrated aqueous hydrochloric acid. The same hydrochloride salt was obtained.

EXAMPLE V 1,8,9,10,1 1,1 l-hexachloro 4,5 diazatetracyclo- [621.1 .0 1 9 doziecene sulfate hydrazo salt as warmed on a steam bath for two hours. At the conclusion of the reaction period the solid matter had dissolved completely and the solution acquired a violet color. It was poured over cracked ice and 4.2 grams of crude sulfate salt was obtained. The crude salt was Washed with hot benzene and 3.9 grams (93%) of the product, M. P. 23540 d., was isolated. Similarly, there can be prepared the nitrate, phosphate, hydrobrornide, oxalate, trilchloroacetate, and other organic and inorganic salts of the novel polycyclic hydrazo bases of the invention by substituting the respective acids for the H2804 and HCl used in this and the preceding example. By isolating the free base and combining it with the appropriate acid, or by metathetical reaction between the sulfate and, for example, the barium salt of the selected acid, salts of the hydrazo compound and weaker acids readily can be prepared, such as the acetate, propionate, benzoate, methylmercaptopropionate, adipate, and salts of alkaryl sulfonates and sulfuric esters of long-chain alcohols.

EXAMPLE VI 4-carbeth0xy 1,8,9,10,11,11 hexachloro 4,5-diazatetracycl0[6.2.1 1 10 -9-d0decene In this example there is illustrated a procedure for preparing monodecarba-lkoxylation products from the compounds of the type illustrated in Examples I, II, and III. In this experiment, 4,5-dicarbethoxy-1,8,9,10,11,11-hexachloro-4,5-diazatetracyclo [621.1 .0 ]-9--dodecene was allowed to stand at room temperature for about hours in admixture with initially an approximately 1.4 M solution of potassium methoxide in methanol. At the end of this time the precipitated potassium carbonate was filtered 01f and washed with ether. The combined washings and fil' An alternative name for this 5,6,7,8,9,9-hexachloro-1,2,3,4,4a,5,8,8a-octahydro-1,4,5,8- dimethanophthalazine.

In an analogous manner 4-carbomethoxy-1,8,9,10,11,11- hexachloro-4,S-diazatetracyclo[6.2.1.1 .0 ]-9-dodecene, melting point 171-172 C., can be prepared from 4,5-dicarbomethoxy-1,8,9,10,11,1l hexachloro 4,5-diazatetracyclo[6.2.1.1 0 ]-9-dodecene.

EXAMPLE VII 1,8,9,10,11,1J-hexachl0r0-4,5-diazatetracyclo- [6.2.1 1 10 -4,9-dodecadiene To a solution of 15.8 grams of 85% KOH in milli-' evaporated to dryness. There remained 19.9 grams of product is 2-carbethoxyssabi crude azo derivative, yield 90%. Analyses: found, 33.5% C, 1.9% H, 57.2% Cl, 7.5% N; calculated for CroHeCleNz, 32.7% C, 1.7% H, 58.0% C1, 7.6% N. Chemical tests confirmed the absence of NH-- groups and the absorption band characteristic of NH-- groups was absent from the infrared absorption spectrum of the product. Upon heating at 80 C. the product evolved nitrogen, given a product melting at 163-64" this provides further confirmation of the azo structure. The structure of the azo derivative can be represented in planar form by the following formula:

An alternative name for this product is 5,6,7,8,9,9-hexachloro 1,4'4a,5,8,8a hexahydro -l,4,5,8 dimethanophthalazine.

EXAMPLE VIII 1 ,8,9,10,1 1 ,1 1 -hexachl0r0-4,5-diazatetrqcyclo- [621.1 .0 1-4-9-d0decadiene The azo derivative, l,8,9,10,11,11-hexachloro-4,5-diazatetracyclo[621.1 .0 ]-4,9-dodecadiene, can also be readily prepared by neutralization of the salts described in Examples IV and V. For example, 3.9 grams (0.008 mole) of the sulfate salt and 1.5 grams (0.008 mole) of barium hydroxide monohydrate were shaken with 20 ml. of water for ten minutes. The product was extracted into ether and recovered upon evaporation of the solvent in a current of dry air. Oxidation of hydrazo to azo compound occurred during this operation, and 2.45 grams (85%) of the latter was obtained. Analyses: found, 32.2% C, 1.8% H, 56.9% C1; calculated for CioHsClsNa, 32.7% C, 1.7% H, 58.0% C1.

EXAMPLE VIIIa By hydrolysis of salts of 1,8,9,10,11,11-hexachloro-4,5- diazatetracyclo[621.1 .0 9 dodecene with weak acids, such as acetic acid, the free base can be liberated. Upon shaking l,8,9,l0,11,l1-hexachloro-4,5-diazatetracyclol6.2.l.l .0 ]-9-dodecene acetate (3 grams) for 4.5 hours with 50 ml. of Water the solid hydrazo base was liberated in 92% yield. The filtered washed and dried product melted at 20205 C. Analyses: found, 57.3% C1, neutralization equivalent 368; calculated for CH8C16NZ, 57.8% Cl, neutralization equivalent 369.

Depending upon the identity of the anion, the salts of 1,8, 9,10,l1,1l-hexachloro-4,5-diazatetracyclo[6.2.1.l .0 9-dodecene will vary in both stability and solubilities. Illustrative salts of this hydrazo base are further illustrated by the following table:

a With decomposition.

EXAMPLE IX 1,8,9,10,1 1,1 1-hexachl0r0-4,S-diazatetracyclo- [621.1 .0 1-4,9-d0decadiene 4-0xide To a solution of 8.3 grams (0.06 mole) of perbenzoic' acid in 235.8 grams of chloroform (by titration) there was added 11.5 grams (0.03 mole) of 1,8,9,10,1'l,l1- hexachloro 4,5 diazatetracyclo[6.2.1.1 3.0 4,9 dodecadiene. After a reaction period of 136 hours at 27, the chloroform solution was washed with 5% sodium hydroxide and then with water. After the solution had been dried over anhydrous sodium sulfate, the solvent was evaporated to near dryness. I-Iexane (15 ml.) was added and 11 grams of crude azoxy derivative was recovered by filtration, M. P. 21540 d. A single recrystallization from ether-cyclohexane gave 10.5 grams (91%) of pure oxide, M. P. 256 d. Analyses: found, 31.6% C, 1.7% H, 55.3% CI, 7.3% N; calculated for CmHeCleNzO, 31.3% C, 1.6% H, 55.6% C1, 7.3% N. Unlike the azo derivative, the oxide is thermally stable, remaining unchanged upon heating at 110 C. for a period of 2 /2 hours.

The novel compounds of this invention, as a class, are useful as new and improved biocides, especially insecticides. In the present specification and claims the term insect is used to mean any of the numerous small invertebrate animals generally having the body more or less obviously segmented, for the most part belonging to the class insecta, comprising six-legged, usually winged forms, as, for example, beetles, bugs, bees, flies and to other allied classes of arthropods whose members are Wingless and usually have more than six legs, as, for example, spiders, mites, ticks, centipedes, and wood lice. By reference to use as an insecticide it is intended to refer to use of preventing, destroying, repelling or mitigating any insects which may be present in any environment whatsoever. Products of this invention are also useful for controlling, mitigating or destroying fungi.

For applying novel products of this invention as insecticides and fungicides, there may be employed any suitable method known in the art for applying toxicants to insects and fungi and their habitats.

The new biocides of this invention may be employed in the form of a solution in a suitable solvent, such as a light petroleum distillate, a chlorinated solvent, or the like. The solutions may be applied to insects and their habitats by spraying, dipping, brushing, and equivalent means, or the solution made up as an emulsifiable concentrate may be dispersed in water with the aid of conventional dispersing or emulsifying agents to provide a dilute aqueous emulsion or suspension which may be applied by spraying, dipping, brushing, and equivalent means. The new products, whether normally liquid or solid, also may be suspended in a non-solvent, e. g., water, with the aid of known suspending or dispersing agents and the multiphase suspension applied to the insects and their habitats. The new toxicants may be applied by means of the aerosol technique.

Soluble salts as illustrated by Examples IV and Vmay be employed as solutions in solvents therefor, such as Water or aqueous alcohols, with addition of wetting agents, if desired, to aid penetration. Such salts have the advantage of chemical stability, as during storage, coupled with high biocidal activity. By adding an alkali, such as lime, sodium hydroxide, or other strong alkali, to the solutions, as in the spray tank, the free hydrazo base can be liberated by reaction of the alkali with the salt. Autoxidation of the free hydrazo base upon exposure to the atmosphere leads to the generation, on the plant foliage or other site of application, of the even more highly toxic azo derivative.

Insecticidal dusts and wettable powders may be pre-' pared by adsorbing the new insecticides on pulverulent solid carriers, such as, for example, clays, calcium carbonate, silica, wood flours, and the like, at concentrations ranging from as little as 1% of the composition to and more by weight of the total composition depending upon the intended use and manner of application.

The new products of this invention may be employed for agricultural purposes, in animal husbandry, and in a wide variety of other and specific applications where there is need for a highly toxic, stable biocide. In general, the new toxicants of this inventionexhibit a relatively high toxicity towards warm-blooded animals and, therefore, should be employed with the precautions in the vicinity of warm-blooded animals although, provided such precautions are taken they can be employed with great efiectiveness in eradicating insects that are noxious to human and other warm-blooded animals. The novel biocides of the invention may also be used for protecting manufactured products from attack by insects and fungi. For example, wood, paper, cloth, felt and similar materials in whatsoever form may beimpregnated or coated with the novel insecticides or compositions comprising the same, or the newtoxicants may be included in appropriate amounts in pastes, glues, paints, varnishes, inks, plastics and synthetic resins, rubber products and the like, to render the same inherently toxic to insects and resistant to attack by insects. When reference is made herein to application of the novel products of this invention to insects or fungi and their habitats, it is intended to include therein application by such perhaps less common means of incorporation in manufactured products as well as the more customary meansof application by spraying or dusting of the toxicant or a composition containing it and a diluent onto the insects or their habitats.

In all of the foregoing applications and compositions, the respective novel products of this invention may be employed as the sole toxic ingredient, or they may be employed in admixture with each other or with other, known toxicants. Among the known insecticides which may be employed in conjunction with the novel products of this invention are, for example, DDT, Aramite, heptachlor, chlordane, dieldrin, aldrin, endrin, rotenone, pyrethrum, benzene hexachloride, allethrin, methoxychlor, parathion, systox, and many others.

By way of example of the outstanding efiectiveness of the new products of this invention as insecticides, the toxicity of representative products of the invention against the common housefly (M usca domestica) was determined using the method described by Y. P. Sun, Journal of Economic Entomology, 43, 45 (1950). The toxicities were compared to that of alpha-chlordane. The toxicities are expressed in terms of the relationship between the amount of alpha-chlordane required to produce 50% mortality of the test insects and the amount of the test material required to produce the same mortality. Assigning alpha-chlordane an arbitrary rating of 100%, the toxicity of the test materials is expressed in terms of the toxicity index which compares the activity on a percentage basis with that of alpha-chlordane. The results shown in the following table were obtained:

TABLE I Compound Toxicity Index Alpha-chlordane (Standard for Comparison) 100 1,8,9,10,11,11 Hexachloro 4,5 diazatetracyclo [6.2.1.1 M

.0 j-Q-dodecene hydrochloride 1270 4 Carbethoxy 1,8,9,10,11,11 hexaehloro 4,5 dlazatetra cyclo[6.2.1.1 -".0 -U-Q-dodecene 368 4,5 Dicarbornethoxy 1,8,9,10,11,11 hexachloro 4,6 diaza tetracyc1o[6.2.1.1 .0 ]-9-dodecene 1530 ,5 Dicarbethoxy 1,8,9,10,11,11 hexachloro 4,5 diaza tetracyclo[6.2.1.1 -.0 J-Q-dodecene 1250 1,8,9,10,11,11 Hexachloro 4,5 diazatetracyclo[6.2.1.1

.0 ]-4,9-dodecadiene 5500 4 Carbomethoxy 1,8,9,10,11,11 hexa tetracyclo[6.2.1.1 -.0 ]-9-dodeeene 1438 4,6 Dicarbobutoxy 1,8,9,10,11,11 hexachloro 4,5 d1

racyclo[6.2.1.1 .0 ]-9-dodeeene 70 1,8,9,10,11,11 Hexachloro 4,5 diazatetracyclo [6.2.1.1 '.0

-9-dodecene sulfate I. 2080 1,8,9,10,11,11 Hexachloro 4,5 diazatetrecyclo [6.2.1.1 -.0

-4,9-dodecadiene 4-oxide 6800 In further tests, representative compounds of the invention were tested against the milkweed bug (Oncopeltus fasciatus) in comparison with chlordane. The tests were carried out by applying measured amounts of the test materials in acetone solution to a square of filter paper and, after the solvent had evaporated, placing the paper on the floor of a small dish in which the test insects were confined. The insects came into contact with the test TABLE II Compound Toxicity Index Chlordane (Standard for Comparison) 1,8,9,10,11,11 Hexachloro 4,5 dlazatetracyclo [6.2

-9-dodecene hydrochloride 4 Carbethoxy 1,8,9,10,1l,11 hexachloro 4,5 diazatetracyc1o[6.2.1.1 -.O ]-9dodecene .1 4,5 Dicarbomethoxy 1,8,9,10,11,l1 hexachloro 4,5 diazatetracyelo[6.2.l.l '.0 ]-9-dodecene 4,5 Dicarbethoxy 1 8,9,10,11,11 hexaehloro 4,5 diazatetracyc1o[6.2.1.1 .0 l-9-dodecene 1,8,9,10,11,11 Hexachloro 4,5 diazatetracyclo [6.2.1.1 "LU -4,9-dodecadiene t 4 Carbomethoxy 1,8,9,1O

cycl0[6.2.1.1 -.0 ]-9-d0decene 1,8,9,10,11,11 Hexachloro 4,5 dia -9-dodeeene sulfate 1,8,9,10,11,11 Hexachloro 4,6 dlazatetracycl -4,9-dodecadiene 4-oxide TABLE III Ratio of Toxicity of 1,8,9,10,11,

11-Hexachloro-4,5-diazatetracyclo [6.2.1. 0 4,9 dodecadiene to that of- Test Test Insect Method Dieldrin Endrin DDT House fly Pomaee fly Large mllkweed bug- Confused flour beetle- Granary weevil Webbing clothes moth. Black carpet beetle Test methods: A-Spray; B-Dry-film, on glass; C-Dry-film, paper; D-Deposit, on cloth.

1,8,9,10,1l,1l hexachloro 4,5 diazatetracyclo- [6.2.1.1 .0 ]-4,9-dodecadiene, although somewhat less toxic than parathion against aphids, has the outstanding advantage that it is virtually non-toxic to the desirable and economically important predaceous lady beetles. This rather surprising selective non-toxicity offers a means for controlling aphids without killing predators.

The residual toxicity of 1,8,9,10,11,1l-hexachloro-4,5- diazatetracyclol 6.2.1.l .0 ]-4,9-dodecadiene is relatively high. For example, one month after .its deposition on filter paper and plywood, the deposits were, respectively, 2.5 and 6 times as toxic to housefiies as equally aged deposits of dieldrin. One of the most noteworthy characteristics of 1,8,9,10,l1,11-exachloro-4,5-diazatetracyclo[6.2.l.l .0 ]-4,9-dodecadiene, however, is that the toxicity of the deposits (to Warm-blooded animals as well as to insects) can be virtually destroyed by heating to sterilization temperatures, such as those that are encountered in canning of foods. This detoxification, which appears to be due to a chemical breakdown occurring to a significant extent only at such relatively high temperatures, offers a means for avoiding to a substantial extent the serious problem that now is encountered with regard to toxic insecticide residues on crops raised to be canned.

graham" 8. 1,8,9,10,1l,11 hexachloro 4,5 diazatetracyclm [6.2.1.1 .0 ]-4,9-dodecadiene.

9. l,8,9,10,ll,ll hexahalo 4,5 diazatetracyclo- [6211 .0 ]-4,9-dodecadiene.

10. 1,8,9,l0,ll,11 hexachloro 4,5 diazatetracyclo- [6.2.l.1 '.O -"]-4,9-dodecadiene 4-oxide.

11. The process which comprises the step of reacting, under heat, (1) the 2,3-diazabicyclo(2.2.l)-5-heptene of the formula R'c--(JNR wherein R is a member selected from the group consisting of hydrogen, lower carbalkoxy, lower carbaroxy, lower carbocyclo-alkoxy, formamido, formamidine, lower alkyl, nitro, and wherein R is selected from the group consisting of hydrogen and lower alkyl with (2) the cyclopentadienoic compound of the formula 05 to "4 all CC wherein the 2, 3, 4 and 5 positions are substituted by a member of the class selected from the group consisting of hydrogen, halogen and lower alkyl, and wherein the 1-position is substituted by a member of the classselected from the group consisting of hydrogen, halogen, lower alkyl and lower alkoxy.

12. A process for the preparation of the product of claim 9 which comprises the steps of reacting, under heat, a lower 2,3-dicarbalkoxy-2,3-diazabicyclo[2.2.1]- heptene with hexalchloro-1,3-cyclopentadiene by 1,4-addition, decarbalkoxylating the product and oxidizing the product of the decarbalkoxylation.

. 16 t V 13. The method of preparing the product of claim 4 which comprises the step of reacting under heat, a lower 2,3-dicarbalkoxy-2,3-diazabicyclo[2.2.l] 5 heptene with hexachloro-1,3-cyclopentadiene by 1,4-addition and de-' carbalkoxylating the product.

14. The method of combatting insects comprising subjecting the insects to the toxic action of a compound defined by claim 21.

15. The method of combatting insects comprising subjecting the insects to the toxic action of 1, 8, 9, 10, 11, llhexachloro 4,5 diazatetracyclo[6.2.1.1 0 4,9- dodecadiene.

16. A composition comprising a compound defined by claim 21 and a carrier as adjuvant therefor.

17. A composition of matter comprising 1,8,9,10,11,l1- hexachloro 4,5 diazatetracyclo[6.2.l.1 .0 4,9- dodecadiene and a carrier as adjuvant therefor.

18. A composition comprising the compound defined by claim 10 and a carrier as adjuvant therefor.

19. A composition comprising a solution of a salt defined by claim 21 in a volatile liquid solvent therefor.

20. 4,5 dicarbalkoxy 1,8,9,l0,l1,11 hex'ahalo 4,5- diazatetracycl0[6.2.1.1 .0 9 dodecene, said carbalkoxy being lower carbalkoxy.

21. The compound of the formula 1m n O l C R 0 J0i1- s 7 6 5 wherein R is the nitrogen containing radical selected from the group consisting of in which R is a member of the class selected from the group consisting of hydrogen, lower carbalkoxy, lower carbaroxy, lower carbocycloalkoxy, formamido, formamidine, lower alkyl, nitroso, lower aryl and nitro groups, and wherein the nucleus is substituted at the 2, 3, 4, 5 and 6 positions by a member of the class selected from the group consisting of hydrogen and lower alkyl, and wherein the 1, 7, 8 and 9 positions are substituted by a member of the class selected from the group consisting of hydrogen, halogen and lower alkyl, and wherein the 10 position is substituted by a member of the class selected from the group consisting of hydrogen, halogen, lower alkyl and lower alkoxy, and salts thereof selected from the group consisting of inorganic acid salts and organic acid salts.

No references cited.

and

Claims

21. THE COMPOUND OF THE FORMULA