Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
  • C07D209/04—Indoles; Hydrogenated indoles
  • C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
  • C07D209/40—Nitrogen atoms, not forming part of a nitro radical, e.g. isatin semicarbazone
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
  • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
  • C07D209/44—Iso-indoles; Hydrogenated iso-indoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D209/56—Ring systems containing three or more rings
  • C07D209/96—Spiro-condensed ring systems

Definitions

• R and R may be hydrogen atoms or hydrocarbon groups containing from one to ten carbon atoms including alkyl, aralkyl, cycloalkyl, ary-l, and alkaryl groups.
• R and R taken together with the carbon atoms to which they are joined may form a carbocyclic ring containing five to six carbon atoms which in turn may have alkyl substituents containing a total of no more than fouradditional carbon atoms.
• R and R taken together with the carbon atoms to which they are joined may form a carbocyclic ring containing five to six carbon atoms which in turn may I have alkyl substituents containing a total ofno more than four additional carbon atoms.
• R and R taken together with the carbon atoms to which they are joined may form a carbocyclic ring containing five to six carbon atoms which ins-turn may have alkyl substituents containing a total of no more than four additional carbon atoms.
• the total number of carbon atoms in the cyanoketone should not exceed twenty-four.
• the preferred embodiments are those in which R and R are alkyl groups, R is a hydrogen atom, and R is a methyl group.
• R R and K may typically individually represent methyl, butyl, octyl, ben z yl, phenylbutyl, cyclopentyl, cyclohexyl, .phenyl, naphthyl, butylphenyl groups,
• Typical cyanoketone reactants include 4-oxopentanonitrile, 3-methyl-4-oxopentanonitrile, 2,2-dimethyl-4-oxopentanonitrile, 2-methy1-2-ethyl-4-oxopentanonitrile,
• A represents a chain, cyclic or acyclic, of at least four carbon atoms
• A is usually hydrocarbon in a ies bassistat s i n l sis a s t s st asr mine, g oan, a ether oxyge at ne;- i sthe l l ta s. W he ke. W it h u as mi s wsr a atoms in A is not especially critical about 24.; is con; ids sd; he.
• P s issl nest imit: n ad ss 5 ar stilsi h rstm' y s-Q ssr ars nitrsg q w u t l em s ss nt.
• a P ou l -m n d Wi h t sasdfislhs sssst at NEVA-Wa is s s s r hat there be, at least four carbon atoms between the; two,
• the reactants of this invention are compounds that are known or prepared by known methods.
• the product of this invention is a specific bis-iminopyrroline having the Formula I.
• the reactants of this invention are mixed and allowed to stand at room temperature or at temperatures up to about 75 C. over prolonged periods of time, a product is formed having the formula and
• the Formula V compounds are usually crystalline solids which, when heated to a range approaching that required for distillation, lose water and are converted to a Formula I product.
• the Formula I compounds, and these of course encompass types II, III, and IV, as discussed heretofore, are predominantly formed under conditions whereby water as formed in the reaction is removed from the reaction medium.
• the preferred method is to conduct the reaction in the presence of an inert volatile organic solvent that forms an azeotrope with water.
• an inert volatile organic solvent that forms an azeotrope with water.
• Useful as a solvent in this respect are benzene, toluene, xylene, heptane, hexane, methylene, chloride, chloroform, and the like.
• the water is removed azeotropically as the reaction progresses, preferably at about 40 C. to 250 C., and very little, if any, of the type V product is formed.
• the reaction is desirably terminated when the substan- 4 tially theoretical amount of water is removed.
• the product may be isolated by distillation under reduced pressure or recrystallization from a solvent, such as isooctane, as desired. If the diprimary amino reactant has been used in excess it has to be separated from the product at the conclusion of the reaction, by conventional methods, or otherwise a diprimary amino addition salt will form.
• the compounds of this invention are valuable for the present purposes.
• the present compounds are useful as fungicides which are non-injurious to plants upon which they are applied.
• Example 1 Hexamethylenediamine (41 parts of an aqueous 75% solution), and toluene (35 parts) are placed in a boiling flask topped by a water separating head and reflux condenser. Toluene (25 parts) is placed in the water separator initially. The reaction mixture is boiled under reflux in order to separate water azeotropically. Water (11 parts) is removed in the course of this preliminary drying operation. There is added 2,2-dimethyl-4-oxopentanonitrile (62.5 parts) when the water separation is completed. Again the mixture is heated to reflux and water is removed azeotropically. The pot temperature remains in the region 154-160 C., under which conditions the theoretical amount of water (9 parts) separates.
• the reaction mixture is stripped of low-boiling materials to a pot temperature of C. at 0.2 mm. absolute pressure.
• the residue (81 parts) is the desired product, 1,8- bis( 2,4,4 trimethyl-2-pyrrolin-5-ylidene)-l,8-diazaoctane having the formula CH3 CH3 1'1 lit Calculated for C H N total nitrogen-17.0%; titratable nitrogen-8.5%. Found: total nitrogen- 16.5%; titratable nitrogen--8.3%.
• the product is 1,7-bis(2,4,4 trimethyl-Z-pyrrolin-S- ylidene) -l,4,7-triazaheptane and has the following structure
• 1,5,8,l2-tetrazadodecane and 2,2- dimethyl 4 oxopentanonitrile give l,l2-bis'(2,4,4-"trimethyl 2 pyrrolin 5 -y1ider 1e) 1,5,8,12 tetrazadodecane
• 1,9 diaza 5 oxanona'ne and l-(2-oxocyclohe xyl) 'cyclohexanecarbonitrile give 1,9 bis(3,3-penta methylene 2,3,4,5,6,7 hexahydroindol 2 ylidene ⁇ 1,9 diaza 5'-'oxanonane
• naphthyl, and alkylphenyl groups of no more than 10 carbon atoms R and R taken collectively with the carbon atoms to which they are joined form a member from the class consisting of a carbocyclic ring of 5 to 6 carbon atoms and one olefinic bond, and said ring having alkyl substituents consisting of a total of no more than 4 carbon atoms, R and R taken collectively with the carbon atoms to which they.
• R3 R -R4] R1 N A in which A represents an alkylene chain of. 4 to 24 carbon I atoms, R and R; are alkyl groups oil to' lO'carb'oii atoms, R is a hydrogen atom, and R is a methyl group; 4.
• the compound whose principal tautomeric form is represented by the formula in which A represents an alkylene chain of 4 to 24 carbon atoms, R and R taken collectively with the carbon atoms to which they are joined represent a'carbocyclic ring. of 5 to 6 carbon atoms having one olefinic bond and R and R are alkyl groups of 1 to 10 carbon atoms. 7
• A represents an alkylene chain of 4 to 24 carbon atoms
• R is an alkyl group of 1 to 10 carbon atoms, R; and R taken collectively with the carbon atoms to which they are joined form a saturated carbocyclic ring of to 6 carbon atoms and R is an alkyl group of 1 to carbon atoms.
• the compound Whose principal tautomeric form is represented by the formula in which A represents an alkylene chain of 4 to 24 carbon atoms, R, is an alkyl group of 1 to 10 carbon atoms, R is an alkyl group of 1 to 4 carbon atoms and R and R taken collectively with the carbon atoms to which they are joined form a saturated carbocyclic ring of 5 to 6 carbon atoms.
• a method according to claim 12 in which the reaction is conducted in the presence of an inert organic volatile solvent that forms an azeotrope with water and the water formed in the reaction is removed azeotropically as the reaction progresses.

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Cited By (1)

Citations (4)

• 0
  • NL NL236637D patent/NL236637A/xx unknown
• 1958
  • 1958-03-03 US US718503A patent/US2975189A/en not_active Expired - Lifetime
• 1959
  • 1959-03-02 GB GB7186/59A patent/GB913933A/en not_active Expired

Patent Citations (4)

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