US3855322A - Aliphatic di-olefinic halides - Google Patents

Aliphatic di-olefinic halides Download PDF

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US3855322A
US3855322A US00206918A US20691871A US3855322A US 3855322 A US3855322 A US 3855322A US 00206918 A US00206918 A US 00206918A US 20691871 A US20691871 A US 20691871A US 3855322 A US3855322 A US 3855322A
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dienoate
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C Henrick
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Zoecon Corp
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/20—Esters of monothiocarboxylic acids
    • C07C327/22—Esters of monothiocarboxylic acids having carbon atoms of esterified thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C205/00—Compounds containing nitro groups bound to a carbon skeleton
    • C07C205/27—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups
    • C07C205/35—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C205/36—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system
    • C07C205/37—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
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    • C07C21/00—Acyclic unsaturated compounds containing halogen atoms
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    • C07C317/00—Sulfones; Sulfoxides
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    • C07C317/08—Sulfones; Sulfoxides having sulfone or sulfoxide groups bound to acyclic carbon atoms of an acyclic unsaturated carbon skeleton
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C317/22—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/02—Thiols having mercapto groups bound to acyclic carbon atoms
    • C07C321/08—Thiols having mercapto groups bound to acyclic carbon atoms of an acyclic unsaturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
    • C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
    • C07C321/28—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/12—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C323/18—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton
    • C07C323/20—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atom of at least one of the thio groups bound to a carbon atom of a six-membered aromatic ring of the carbon skeleton with singly-bound oxygen atoms bound to carbon atoms of the same non-condensed six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/02—Monothiocarboxylic acids
    • C07C327/04—Monothiocarboxylic acids having carbon atoms of thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C327/10—Monothiocarboxylic acids having carbon atoms of thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of an acyclic unsaturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/203—Unsaturated compounds containing keto groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/58—Preparation of carboxylic acid halides
    • C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof

Definitions

  • each of m and n is zero or the positive integer one, two or three;
  • each of R? and R is lower alkyl
  • R is alkyl
  • each of R R R R R and R is hydrogen or lower alkyl
  • X is bromo, chloro, fluoro or iodo.
  • the compounds of formula A are usefulfor the control of insects.
  • the utility of these compounds as insect control agents is believed to be attributable to their juvenile hormone activity. They are preferably applied to the immature insect, namely' during the embryo, larvae or pupae stage in view of their effect on metamorphosis and otherwise cause abnormal development leading to death orinability to reproduce.
  • Hemipteran such as Lygaeidae, Miridae and Pyrrhocoridae
  • Lepidopteran such as pyralidae, Noctuidae' and Gelechiidae
  • Coleopteran such as Tenebrionidae, Crysomelidae and Dermestidae
  • Dipteran such as mosquitosand flies
  • Homopteran such as aphids
  • Suitable halogenation methods include the reaction of an allylic alcohol of formula C with a halogenation agent, such as a phosphorus trihalide or phosphorus pentahalide in an organic solvent inert to the reaction.
  • Other suitable procedures include conversion of the allylic alcohol of formula C into the respective tosylate or mesylate followed by treatment with an alkali halide,
  • the fluorides can be prepared by reaction of an iodide or bromide with silver fluoride.
  • the allylic alcohols of formula C can be prepared by reduction of an afi-unsaturated acid or ester of formula B using lithium aluminum hydride, and the like, in an organic solvent inert. to the reaction.
  • the acids and esters of formula B can be prepared as described in application Ser. No. 187,898, filed Oct; 8, 1971, now U.S. Pat. No. 3,752,843, the disclosure of which is incorporated by reference.
  • R - is hydrogen-or lower alkyl
  • insects The compounds can be applied at low dosage levels of the order of 0.001 ug. to 25.0 pg. per insect.
  • suitable carrier substances include liquid or solid carriers, such as water, acetone, xylene, mineral or vegetable oils, talc, venniculite, natural and synthetic resins and silica.
  • - Treatment of insects in accordance with the present invention is accomplished by spraying, dusting or exposing the insects to the vapor of the compounds of formula A. Generally, a concentration of less than 25% of the active compound is employed.
  • the formulations can include insect attractants, emulsifying agents or wetting agents to assist in the application and effectiveness of the active ingredient. In the application of thecompounds, there is generally employed a mixture of the C-2,3 trans and cis isomers.
  • the allylic halides of formula A can .be prepared from the respective allylic alcohol precursor of formula C by halogenation:
  • each of R and R is hydrogen, alkyl, alkenyl, cycloalkyl, hydroxyalkyl, alkoxyalkyl, aryl, aralkyl, or
  • EXAMPLE 1 Sodium methoxide (from 200 mg. sodium and 12 ml. methanol) is added dropwise to a stirred solution of 1.8 g. of trans diethyl 3-ethoxycarbonyl-2-methylprop-2- enyl phosphonate and 1 g. of 3,7-dimethy1-1-nonanal in 50 ml. of dimethylformamide under nitrogen. The reaction mixture is left for 1 hour at room temperature and then water is added followed by extraction with ether. The ethereal extracts are washed with brine, dried and evaporated to yield trans/cis methyl 3,7,1l-trimethy1- trideca-2,4-dienoate. The isomeric mixture can be chromatographed on silica or distilled for purification. The isomeric mixture is predominantly trans at C-2,3.
  • EXAMPLE 2 To a mixture of 250 mg. of sodium hydride in 2 ml. of tetrahydrofuran, with ice-cooling, is added 1.6 g. of trans diethyl 3-ethoxycarbonyl-2-methylprop-2-enyl phosphonate in 5 ml. of tetrahydrofuran. Temperature is allowed to rise to room temperature and after 30 minutes, 0.95 g. of 3-ethy1-7-methyl-l-nonanal is added. After about 1 hour at room temperature, the
  • EXAMPLE 3 To 125 mg. of a 57% dispersion of sodium hydride in oil is added pentane. The pentane is removed and the sodium hydride washed several times with pentane. To the washed sodium hydride is added 582 mg. of diethyl acetylmethylphosphonate (11A; R is ethyl, R is methyl) in 5 ml. of tetrahydrofuran at -l0 under argon. After several minutes, the solution is transferred to a solution of 425 mg. of 3,7-dimethyloctan-l-al in about 4 ml. of dry tetrahydrofuran under argon over a period of about 20 minutes at room temperature. After about 2 hours, water is added followed by addition of ether and the layers separated. The organic layer is washed with saturated sodium chloride, dried over sodium sulfate and evaporated under reduced pressure to yield 6,l0- dimethylundec-3-en-2-one
  • EXAMPLE 4 32.3 Grams of sodium hydride (57% in oil) is placed in a dry, one liter, 3-neck flask (fitted with a nitrogen inlet) and washed three times ml. each) with dry pentane under nitrogen, carefully decanting only the solvent each time, into a beaker of ethanol. 400 Milliliters dry tetrahydrofuran is then added, the mixture cooled to 0, and 156.0 g. of diethyl carbethoxymethyl phosphonate is added under nitrogen. The solution is stirred for 0.5 hour after addition is complete, and then g. of 6,10-dimethylundec-3-en-2-one in 250 ml.
  • EXAMPLE 5 A mixture of l g. of trans/cis methyl 3,7,1 1- trimethy1dodeca-2,4-dienoate,- 60 ml. of methanol, 0.5 g. of sodium hydroxide and 6 m1. of water is stirred at about 30 for about 56 hours. The mixture is then diluted with water, neutralized and extracted with ether. The organic phase is washed with water, driedover sodium sulfate and evaporated to yield trans/cis 3,7,11- trimethyldodeca-2,4-dienoic acid.
  • EXAMPLE 6 To 1.6 g. of sodium hydride (57% in oil dispersion) in a 500 m1., 3-neck flask, fitted with a nitrogen inlet, is added 25 to 50 ml. of dry hexane or pentane and the mixture swirled under nitrogen. The NaH is allowed to settle and the solvent carefully decanted into a beaker containing ethanol. This 'rinsing process is repeated twice and 100 ml. of dry tetrahydrofuran is added via syringe or pipet. Mixture is cooled in an ice-bath and 9.0 g. triethylphosphonacetate (dried over molecular sieves) is added via addition funnel over a 10 minute period.
  • EXAMPLE 7 41 Grams of 3,7-dimethy1octan-l-al and 80 g. of re- EXAMPLE 8 One gram of triphenylphosphineacetylmethylene and 425 mg. of 3,7-dimethylnonan-1-al are dissolved in 10 ml. toluene and refluxed under nitrogen overnight. The toluene is distilled off and the formed triphenylphosphine oxide crystallized by addition of pentane. Filtration and evaporation of the pentane gives a residue,
  • EXAMPLE 9 To a mixture of one g. of 3,7-dimethyl-1-octanaland- 1.5 g. of diethyl 3-ethoxycarbonyl-2-methylprop-2- enylphosphonate and 50 ml. of dimethylformamide, under nitrogen, is slowly added sodium ethoxide (prepared from 200 mg. of sodium and 12 ml. of ethanol).
  • Each of the methyl esters under column V is hydrolyzed to the free acid using the procedure of Example 5 or by refluxing for several hours.
  • ethyl 3 ,7 ,1 I l l-tetramethyldodeca-2,4-dienoate, ethyl 3,7,1 1 1 1-tetramethyltrideca-2,4-dienoate, ethyl 3,7, l0,10-tetramethylundeca-2,4-dienoate, ethyl 3 ,7 l 2,12-tetramethyltrideca-2,4-dienoate, and
  • EXAMPLE 16 EXAMPLE 1? Sodium methoxide (1.2 g. of sodium and 30 ml. of methanol) is added slowly to a mixture of g. of dihydrocitronellal and g. of diethyl 3-methoxycarbonyl- 2-methylprop-2-enyl phosphonate (about 77% trans) in 50 ml. of dimethylfonnamide, under nitrogen and at about 0, with stirring. After addition is complete, the reaction is left three hours at room temperature and then worked up by extraction with hexane/ether to yield cis/trans methyl 3,7,1 l-trimethyldodeca-2,4- dienoate, mostly the trans, trans isomer.
  • EXAMPLE 18 To a mixture'of 1.5 g. of dihydrocitronellal, 2.7 g. of diethyl 3-ethoxycarbonyl-2-methylprop-2-enyl phosphonate and 5 ml. of dimethylformamide, under nitrogen and at 0, with stirring, is added slowly sodium methoxide (250 mg. sodium and 5 ml. of methanol). After addition is complete, the reaction is left two hours at room temperature and then worked up by extraction with ether/hexane to yield methyl 3,7,11- trimethyldodec'a-2,4-dienoate.
  • sodium methoxide 250 mg. sodium and 5 ml. of methanol
  • EXAMPLE 19 To a mixture of 30 g. of dihydrocitronellal, 44 g. of diethyl 3-ethoxycarbonyl-2-ethylprop-2-eny1 phosphonate and 200 ml. of dimethylformamide, under nitrogen at 0 and with stirring, is added slowly sodium ethoxide (4.6 g. sodium in 100 ml. of ethanol). After addition is complete, the reaction is left at room temperature for two hours and then worked up by extraction with hexane to yield ethyl 3-ethyl-7,l l-dimethyldodeca-2,4-dienoate.
  • sodium ethoxide 4.6 g. sodium in 100 ml. of ethanol
  • EXAMPLE 20 To 350 ml. of ethanol, 105 ml. of water and ml. of 50% aqueous sodium hydroxide is added 46.5 g. of ethyl 3,7,11-trimethyldodeca-2,4-dienoate (40% cis, trans and 60% trans, trans). The mixture is refluxed for about 19 hours. After cooling, ethanol is removed under reduced pressure and water added followed by extraction with ether to yield 3,7,1 l-trimethyldodeca- 2,4-dienoic acid containing about 58% trans, trans isomer.
  • EXAMPLE 22 A. Eighty ml. of a 3M solution of methylmagnesium bromide in ether is added slowly to 31 g. of dihydrocitronellal in 250 ml. of dry ether. The mixture is heated at reflux for about 1 hour, cooled to 0 and treated with saturated aqueous ammonium chloride until reaction subsides. The organic layer is separated and the aqueous layer extracted with ether. The organic layer and ether extracts are combined, washed with water and brine and dried over magnesium sulfate. Evaporation of the solvent gives 4,8-dimethylnonan-2-ol.
  • esters of this example and Example 22 can be hydrolyzed to the free acid according to the procedure of Example 5 or 20.
  • esters listed below is reduced using lithium aluminum hydride to yield the respective allylic alcohol.
  • EXAMPLE 25 To a mixture of 4 g. of 3,7,1 1,1 l-tetramethyltrideca- 2,4-dien-l-ol and 25 ml. of ether at 20 is added a solution of ml. of phosphorus tribromide in 18 ml. of ether over about minutes. The mixture is stirred at 0 for approximately one hour and then poured onto ice and extracted with pentane. The organic phase is washed with aqueous sodium bicarbonate, water and then brine, dried over magnesium sulfate and evaporated to yield l-bromo-3,7,ll,ll-tetramethyltrideca- 2,4-diene.
  • novel allylic chlorides are prepared, e.g.
  • EXAMPLE 26 Ten grams of l-bromo-3,7,ll-trimethyldodeca-2,4- diene is mixed with 50 ml. of benzene, cooled to 5-10 and saturated with ammonia. The resulting mixture is stirred for 4 hours allowing the temperature to rise to about 20 while maintaining dry conditions. The mixture is washed with dilute sodium hydroxide and then evaporated under reduced pressure to yield 3,7,1 1- trimethyldodeca-2,4-dieny1amine.
  • EXAMPLE 27 Five grams of l-bromo-3,7,l l-trimethyldodeca-2,4- diene in 25 ml. of benzene is mixed with 4 g. of diethylamine and the mixture stirred for about 3 hours. Methylene chloride (50 ml.) is added and the mixture washed with dilute sodium hydroxide and then water and evaporated to yield N,N-diethyl 3,7,1l-trimethyldodeca-2,4-dienylamine.
  • the compounds of this invention achieve control by reason of their ability to inhibit metamorphosis, inhibit reproduction due to abnormal development, break diapause'at an unfavorable time, or act as a direct insecticide, particularly at the embryo stage and larvae stage.
  • Treatment of insects in accordance with the present invention can be achieved via ingestion of the active compound in the normal food of the insect and by topical application, that is, by contact of the epidermis of the insect as by spraying the insect and habitat of the insect or exposure to vapors of the active compound which penetrate into the insect.
  • the compounds of the present invention can be used in conjunction with other juvenile hormone active substances and conventional insecticides to obtainv a broader spectrum of activity or to provide more immediate effect on very heterogeneous populations.
  • Typical insecticides which may be combined with the compounds of the present invention are Malathion, Sevin,
  • EXAMPLE 28 To a solution of 5.2 g. of 3,7,1 l-trimethyldodeca-2,4- dien-l-ol and 40 ml. of ether, cooled to 50, is added 2.45 g. of phosphorus tribromide in 5 ml. of ether over about 20 minutes. The reaction mixture is stirred for two hours, poured onto ice and extracted with ether. The ethereal extracts are combined, washed with 10% sodium carbonate, water and saturated sodium chloride, dried over sodium sulfate and solvent evaporated under reduced pressure to yield l-bromo-3,7,l l-trimethyldodeca-2,4-diene.
  • EXAMPLE 29 To 250 ml. of anhydrous pyridine, cooled in an icebath, is added 35.2 g. of p-toluenesulfonyl chloride. When the sulfonyl chloride is dissolved, 34 g. of 3,7,1 1- trimethyldodeca-2,4-dien-l-ol is added with 20 ml. of anhydrous pyridine. The reaction mixture is stirred at about 5-10 for 24 hours. Then 40 ml. of cold water is added and the mixture stirred for one hour at ice temperature. The mixture is extracted with pentane.
  • the pentane extracts are washed with HC] and water, dried over potassium sulfate/potassium carbonate and concentrated under reduced pressure.
  • the concentrate is taken up in 50 ml. of dry acetone and added to a solution of 36 g. of dry sodium iodide in 150 m1. of dry acetone.
  • the reaction mixture is stirred at room temperature for about 20 hours and then filtered.
  • the filtrate is concentrated and taken up in pentane.
  • the pentane solution is washed with water, dried over sodium sulfate and evaporated to yield 3,7,1l-trimethyldodeca-2,4-dienyl iodide, which can be purified by chromatography.
  • EXAMPLE 30 A mixture of 33 g. of l-bromo-3,7,l l-trimethyldodeca-2-,4-diene and 100 ml. of dry ethylene glycol in slowly added, with stirring, to a suspension of 11.5 g.
  • the same compound can be prepared by using an equivalent amount of silver fluoride in place of potassium fluoride.

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Abstract

Novel aliphatic hydrocarbon di-olefinic halides and derivatives thereof, intermediates therefor, syntheses thereof and the control of insects.

Description

ite States atent [191 260/465 R, 260/563 R, 260/577, 260/583 R, 260/584 .R, 260/586 R, 260/593 R, 260/601 R, 260/611 R, 260/614 R, 260/632 R, 260/653.3,
Henrick 1 Dec. 17, 1974 ALIPHATIC Dl-OLEFINIC HALIDES [51] Int. Cl. C07c 21/04 Inventor: Cli e A. "e ic o Alto, Fleld of Search R [73] Assignee: ggficfon Corporation, Palo Alto, [56] References Cited 22 H d. D UNITED STATES PATENTS 1 3,706,733 12/1972 Henrick et al. .I 260/654 R [21] App]. N0.: 206,918 Related A D t Primary ExaminerLeon Zitver v [63] Continuation-impart o f s e r :1 T8: 898 Oct 8 Assistant Examiner-Joseph Boska 1971, Pat. No. 3,752,843, and Ser. No. 111,873, Feb: Attorney. Agent 3' Frm Dna|d Encksfm;
1, 1971 abandoned 3 Lee-Lou1se H. Pr1est [52] US. Cl. 260/654 R, 260/247, 260/268 R [57] ABSTRACT thereof and the control of insects.
3 Claims, No Drawings compounds, intermediates therefor, synthesis thereof and the control of insects. More particularly, the novel di-olefinic compounds of the present invention are represented by the following formula (A):
each of m and n is zero or the positive integer one, two or three;
each of R? and R is lower alkyl;
R is alkyl;
each of R R R R and R is hydrogen or lower alkyl; and
X is bromo, chloro, fluoro or iodo.
The compounds of formula A are usefulfor the control of insects. The utility of these compounds as insect control agents is believed to be attributable to their juvenile hormone activity. They are preferably applied to the immature insect, namely' during the embryo, larvae or pupae stage in view of their effect on metamorphosis and otherwise cause abnormal development leading to death orinability to reproduce. These-compounds are effective control agents for Hemipteran, such as Lygaeidae, Miridae and Pyrrhocoridae; Lepidopteran, such as pyralidae, Noctuidae' and Gelechiidae; Coleopteran, such as Tenebrionidae, Crysomelidae and Dermestidae; Dipteran, such as mosquitosand flies; Homopteran, such as aphids; and other Suitable halogenation methods include the reaction of an allylic alcohol of formula C with a halogenation agent, such as a phosphorus trihalide or phosphorus pentahalide in an organic solvent inert to the reaction. Other suitable procedures include conversion of the allylic alcohol of formula C into the respective tosylate or mesylate followed by treatment with an alkali halide,
such as lithium bromide, lithium iodide, lithium chloride, sodium iodide, sodium bromide, and the like, to prepare the respective halide. The fluorides can be prepared by reaction of an iodide or bromide with silver fluoride.
The allylic alcohols of formula C can be prepared by reduction of an afi-unsaturated acid or ester of formula B using lithium aluminum hydride, and the like, in an organic solvent inert. to the reaction. The acids and esters of formula B can be prepared as described in application Ser. No. 187,898, filed Oct; 8, 1971, now U.S. Pat. No. 3,752,843, the disclosure of which is incorporated by reference.
' wherein, R -is hydrogen-or lower alkyl.
insects. The compounds can be applied at low dosage levels of the order of 0.001 ug. to 25.0 pg. per insect. Suitable carrier substances include liquid or solid carriers, such as water, acetone, xylene, mineral or vegetable oils, talc, venniculite, natural and synthetic resins and silica.- Treatment of insects in accordance with the present invention is accomplished by spraying, dusting or exposing the insects to the vapor of the compounds of formula A. Generally, a concentration of less than 25% of the active compound is employed. The formulations can include insect attractants, emulsifying agents or wetting agents to assist in the application and effectiveness of the active ingredient. In the application of thecompounds, there is generally employed a mixture of the C-2,3 trans and cis isomers.
In the description hereinafter, each of RR R -R, X, m and his as defined above, unless otherwise specified.
The allylic halides of formula A can .be prepared from the respective allylic alcohol precursor of formula C by halogenation:
The allylic bromides, chlorides and iodides of formula A are'useful intermediates for the synthesis of amines of the formula:
Ra R14 R2 R1: R12 R1 Rs l 1 l I l I R4 o-oH- cHnn-cm-oH- cH, ,,,-o=o-o=oH-oH,-N
wherein each of R and R is hydrogen, alkyl, alkenyl, cycloalkyl, hydroxyalkyl, alkoxyalkyl, aryl, aralkyl, or
' when taken together with the nitrogen atom to'which a mixture of isomers is suitably employed for the control of insects, such as a mixture containing the trans(2), trans(4) isomer and the cis (2), trans(4) isomer. In the specific examples hereinafter, when isomerism is not specified, it is understood to include a mixture of isomers which, if desired, can be separated using known separation methods. Hereafter, when only one designation of configuration is given, the designation refers to position 02,3 and the configuration is taken to be trans at position C-4,5 when not otherwise specified. The use of trans/cis and cis/trans is with reference to position C-2,3 and indicates a mixture of isomers.
The following examples are provided to illustrate the practice of the present invention. Temperature is given in degrees Centigrade.
EXAMPLE 1 Sodium methoxide (from 200 mg. sodium and 12 ml. methanol) is added dropwise to a stirred solution of 1.8 g. of trans diethyl 3-ethoxycarbonyl-2-methylprop-2- enyl phosphonate and 1 g. of 3,7-dimethy1-1-nonanal in 50 ml. of dimethylformamide under nitrogen. The reaction mixture is left for 1 hour at room temperature and then water is added followed by extraction with ether. The ethereal extracts are washed with brine, dried and evaporated to yield trans/cis methyl 3,7,1l-trimethy1- trideca-2,4-dienoate. The isomeric mixture can be chromatographed on silica or distilled for purification. The isomeric mixture is predominantly trans at C-2,3.
methyl 3 ,7, l 0,1 l -tetramethy1trideca-2,4-dienoate and methyl 3,6,8,9-tetramethy1deca-2,4-dienoate, re-
spectively.
The foregoing procedure is repeated using sodium ethoxide in place of sodium methoxide to yield trans/- cis ethyl 3,7,1 l-trimethy1trideca-2,4-dienoate.
EXAMPLE 2 To a mixture of 250 mg. of sodium hydride in 2 ml. of tetrahydrofuran, with ice-cooling, is added 1.6 g. of trans diethyl 3-ethoxycarbonyl-2-methylprop-2-enyl phosphonate in 5 ml. of tetrahydrofuran. Temperature is allowed to rise to room temperature and after 30 minutes, 0.95 g. of 3-ethy1-7-methyl-l-nonanal is added. After about 1 hour at room temperature, the
mixture is extracted with ether. The ethereal extracts are washed with brine, dried and evaporated to yield trans/cis ethyl 3,1 1-dimethyl-7-ethy1-trideca-2,4- dienoate (about 1:1 mixture of C-2,3 trans and cis isomers).
EXAMPLE 3 To 125 mg. of a 57% dispersion of sodium hydride in oil is added pentane. The pentane is removed and the sodium hydride washed several times with pentane. To the washed sodium hydride is added 582 mg. of diethyl acetylmethylphosphonate (11A; R is ethyl, R is methyl) in 5 ml. of tetrahydrofuran at -l0 under argon. After several minutes, the solution is transferred to a solution of 425 mg. of 3,7-dimethyloctan-l-al in about 4 ml. of dry tetrahydrofuran under argon over a period of about 20 minutes at room temperature. After about 2 hours, water is added followed by addition of ether and the layers separated. The organic layer is washed with saturated sodium chloride, dried over sodium sulfate and evaporated under reduced pressure to yield 6,l0- dimethylundec-3-en-2-one.
EXAMPLE 4 32.3 Grams of sodium hydride (57% in oil) is placed in a dry, one liter, 3-neck flask (fitted with a nitrogen inlet) and washed three times ml. each) with dry pentane under nitrogen, carefully decanting only the solvent each time, into a beaker of ethanol. 400 Milliliters dry tetrahydrofuran is then added, the mixture cooled to 0, and 156.0 g. of diethyl carbethoxymethyl phosphonate is added under nitrogen. The solution is stirred for 0.5 hour after addition is complete, and then g. of 6,10-dimethylundec-3-en-2-one in 250 ml. dry tetrahydrofuran is added over about 0.5 hour period at room temperature under nitrogen. The mixture is stirred overnight at 60 and then poured into saturated NaCl at 0 and extracted with ether (3 X 200 ml.), the organic layers dried (CaSO and concentrated under reduced pressure to yield trans/cis ethyl 3,7,1 l-trimethyldodeca-2,4-dienoate which can be separated into the individual C-2, 3 trans and cis isomers using gas-liquid chromatography or fractional distillatron.
EXAMPLE 5 A mixture of l g. of trans/cis methyl 3,7,1 1- trimethy1dodeca-2,4-dienoate,- 60 ml. of methanol, 0.5 g. of sodium hydroxide and 6 m1. of water is stirred at about 30 for about 56 hours. The mixture is then diluted with water, neutralized and extracted with ether. The organic phase is washed with water, driedover sodium sulfate and evaporated to yield trans/cis 3,7,11- trimethyldodeca-2,4-dienoic acid.
EXAMPLE 6 To 1.6 g. of sodium hydride (57% in oil dispersion) in a 500 m1., 3-neck flask, fitted with a nitrogen inlet, is added 25 to 50 ml. of dry hexane or pentane and the mixture swirled under nitrogen. The NaH is allowed to settle and the solvent carefully decanted into a beaker containing ethanol. This 'rinsing process is repeated twice and 100 ml. of dry tetrahydrofuran is added via syringe or pipet. Mixture is cooled in an ice-bath and 9.0 g. triethylphosphonacetate (dried over molecular sieves) is added via addition funnel over a 10 minute period. Stir an additional one-half hour. The solution of the above anion is transferred via syringe to a ml. addition funnel (with pressure equalizing arm) and is added over about one hour to 6.73 g. of 6,10-dimethyldodec-3-en-2-one at room temperature with stirring. The homogenous solution is then refluxed overnight (18-24 hours). The mixture is then poured into saturated sodium chloride at 0 and extracted with ether. The organic phase is dried and concentrated under reduced pressure to yield trans/cis ethyl 3,7,1 1- trimethyltrideca-2,4-dienoate, which can be purified by chromatography or distillation.
EXAMPLE 7 41 Grams of 3,7-dimethy1octan-l-al and 80 g. of re- EXAMPLE 8 One gram of triphenylphosphineacetylmethylene and 425 mg. of 3,7-dimethylnonan-1-al are dissolved in 10 ml. toluene and refluxed under nitrogen overnight. The toluene is distilled off and the formed triphenylphosphine oxide crystallized by addition of pentane. Filtration and evaporation of the pentane gives a residue,
which is further purified by preparative, thin-layer chromatography, with the plate eluted with 15% ethyl acetatezhexane. Removal of the UV active band gives 6,10-dimethyldodec-3-en-2-one.
EXAMPLE 9 To a mixture of one g. of 3,7-dimethyl-1-octanaland- 1.5 g. of diethyl 3-ethoxycarbonyl-2-methylprop-2- enylphosphonate and 50 ml. of dimethylformamide, under nitrogen, is slowly added sodium ethoxide (prepared from 200 mg. of sodium and 12 ml. of ethanol).
The mixture is allowed to stand at room temperature for one hour and then is worked up with ether. The ethereal extracts are dried, concentrated and then chromatographed on silica plates eluting with hexane/ether (5% ether) to yield ethyl 3,7,11-trimethyl dodeca-2,4-dienoate which is predominantly trans at position C-2,3.
EXAMPLE 10 Following the procedure of Example 2 or 9 each of the aldehydes under column I is reacted with the carbanion of diethyl 3-ethoxycarbonyl-2-methylprop-2-enyl phosphonate to produce the corresponding ethyl esters under column 11.
3 ,7-dimethyloctan- 1 -al,
3,7 -dimethy1nonan-1-a1, 3-ethyl-7-methy1nonan-1-a1, 3 ,6-dimethylheptan- 1 -a1, 2,5-dimethylhexan- 1 -al, 2,5-dimethylheptan- 1 -al 4,8-dimethylnonan- 1 -al, 4,9-dimethyldecan-1-a1, and 3,9-dimethyldecan- 1 -al.
ethyl 3,7,1 1-trimethyldodeca-2,4-dienoate, ethyl 3,7,1 l-trimethyltrideca-2,4-dienoate, ethyl 3, 1 1-dimethyl-7-ethyltrideca-2,4-dienoate, ethyl 3 ,7, l O-trimethylundeca-Z,4-dienoate,
ethyl 3,6,9-trimethyldeca-2,4-dienoate, ethyl 3,6,9-trimethylundeca-2,4-dienoate, ethyl 3,8 ,1 2-trimethyltrideca-2,4-dienoate, ethyl 3,8,13-trimethy1tetradeca-2,4-dienoate, and ethyl 3,7, 1 3-trimethyltetradeca-2,4-dienoate.
EXAMPLE 11 Each of the esters under column 11 is hydrolyzed I using the procedure of Example 5 or by refluxing for about 20 hours to produce the corresponding free acid under column III.
Ill
3,7,1 1-trimethyldodeca-2,4-dienoic acid,
3,7,1 1-trimethy1trideca-2,4-dienoic acid,
3, 1 1-dimethyl-7-ethyltrideca-2,4-dienoic acid, 3,7, 10=trimethylundeca-2,4-dienoic acid, 3,6,9-trimethyldeca-2,4-dienoic acid, 3,6,9-trimethylundeca-2,4-dienoic acid,
3 ,8, l2-trimethy1trideca-2,4-dienoic acid,
3,8, l 3-trimethyltetradeca-2,4-dienoic acid, and 3,7,1 3-trimethyltetradeca-2,4-dienoic acid.
EXAMPLE 12 Each of the aldehydes under column I is used as the aldehyde starting material in the procedure of Example 3, 7 or 8 to produce the corresponding ketone under column IV.
6,10-dimethylundec-3'en-2-one, 6, IO-dimethyldodec-3-en-2-one, 6-ethyl-10-methyldodec-3-en-2-one, 6,9-dimethyldec-3-en-2-one, 5,8-dimethylnon-3-en-2-one, 5,8-dimethy1dec-3-en-2-one,
7, l 1-dimethyldodec-3-en-2-one, 7,1Z-dimethyltridec-3-en-2-one, and 6,12-dimethyltridec-3-en-2-one.
EXAMPLE I 3 Each of the ketones under column IV is converted into the corresponding methyl ester under column V using the procedure of Example 4 or 6.
methyl 3,7,1 l-trimethyldodeca-2,4-dienoate,
methyl 3,7,1 1-trimethyltrideca-2,4-dienoate,
methyl 3,1 l-dimethy1-7-ethyltrideca-2,4-dienoate,
methyl 3 ,7, 10-trimethylundeca-Z,4-dienoate, methyl 3,6,9-trimethyldeca-2,4-dienoate,
methyl 3,6,9-trimethy1undeca-2,4-dienoate,
methyl 3,8, 1 Z-trimethyltrideca-2,4-dienoate,
methyl 3,8, l 3-trimethyltetradeca-2,4-dienoate, and
methyl 3,7, l 3-trimethyltetradeca-2,4-dienoate.
Each of the methyl esters under column V is hydrolyzed to the free acid using the procedure of Example 5 or by refluxing for several hours.
EXAMPLE 14 Following theprocedure of either Example 1, 2 or 9, each of the aldehydes under column VII is convertedinto the respective ester under column VIII.
VII
3,7,7-trimethyloctan- 1 -al,
3 ,7,7-tn'methylnonan- 1 -al,
3 ,6,6-trimethylheptan- 1 -al, 3,8,8-trimethylnonan- 1 -a1, and 4, 8 ,S-trimethylnonan- 1 -al.
VIII
ethyl 3 ,7 ,1 I l l-tetramethyldodeca-2,4-dienoate, ethyl 3,7,1 1 1 1-tetramethyltrideca-2,4-dienoate, ethyl 3,7, l0,10-tetramethylundeca-2,4-dienoate, ethyl 3 ,7 l 2,12-tetramethyltrideca-2,4-dienoate, and
ethyl 3,8,1 2, 12-tetramethyltrideca-2,4-dienoate.
EXAMPLE 15 The aldehydes under column VII are used as the starting material in the process of Example 3, 7 or 8 to prepare the respective ketone under column IX.
6, l 0, l O-trimethylundec-3-en-2-one,
6, l 0, l -trimethyldodec-3-en-2-one, 6,9,9-trimethyldec-3-en-2-one,
6,1 1,1 1-trimethyldodec-3-en-2-one, and 7,1 1,1 1-trimethyldodec-3-en-2-one.
EXAMPLE 16 EXAMPLE 1? Sodium methoxide (1.2 g. of sodium and 30 ml. of methanol) is added slowly to a mixture of g. of dihydrocitronellal and g. of diethyl 3-methoxycarbonyl- 2-methylprop-2-enyl phosphonate (about 77% trans) in 50 ml. of dimethylfonnamide, under nitrogen and at about 0, with stirring. After addition is complete, the reaction is left three hours at room temperature and then worked up by extraction with hexane/ether to yield cis/trans methyl 3,7,1 l-trimethyldodeca-2,4- dienoate, mostly the trans, trans isomer.
EXAMPLE 18 To a mixture'of 1.5 g. of dihydrocitronellal, 2.7 g. of diethyl 3-ethoxycarbonyl-2-methylprop-2-enyl phosphonate and 5 ml. of dimethylformamide, under nitrogen and at 0, with stirring, is added slowly sodium methoxide (250 mg. sodium and 5 ml. of methanol). After addition is complete, the reaction is left two hours at room temperature and then worked up by extraction with ether/hexane to yield methyl 3,7,11- trimethyldodec'a-2,4-dienoate.
EXAMPLE 19 To a mixture of 30 g. of dihydrocitronellal, 44 g. of diethyl 3-ethoxycarbonyl-2-ethylprop-2-eny1 phosphonate and 200 ml. of dimethylformamide, under nitrogen at 0 and with stirring, is added slowly sodium ethoxide (4.6 g. sodium in 100 ml. of ethanol). After addition is complete, the reaction is left at room temperature for two hours and then worked up by extraction with hexane to yield ethyl 3-ethyl-7,l l-dimethyldodeca-2,4-dienoate.
EXAMPLE 20 To 350 ml. of ethanol, 105 ml. of water and ml. of 50% aqueous sodium hydroxide is added 46.5 g. of ethyl 3,7,11-trimethyldodeca-2,4-dienoate (40% cis, trans and 60% trans, trans). The mixture is refluxed for about 19 hours. After cooling, ethanol is removed under reduced pressure and water added followed by extraction with ether to yield 3,7,1 l-trimethyldodeca- 2,4-dienoic acid containing about 58% trans, trans isomer. Conversion of the thus-obtained acid to the S-benzyl-isothiouranium salt recrystallized from aqueous methanol, and regeneration of the acid with etheraqueous hydrochloric acid provides crystalline trans, trans 3,7,1 1-trimethyldodeca-2,4-dienoic acid.
EXAMPLE 21 By use of the procedures hereinabove, see Example 16 and 17, for example, each of the aldehydes under column XVIII is reacted with the carbanion of diethyl 3-ethoxycarbonyl-2-methylprop-2-enyl phosphonate to prepare the respective ethyl ester under column XIX.
XVIII 3 ,7-dimethyldecanl-al,
3 ,7-dimethylundecan- 1 -al,
3 ,5 ,-trimethylheptanl-al, 3,8-dimethylnonan- 1 -al, 2,6-dimethylheptan- 1 -al, 4,7,8-trimethylnonan- 1 -al, 4,8-dimethyldecan-1-al, 2,9-dimethyldecanl-al, 2,5,6-trimethylheptan- 1 -al, 2,6,6-trimethylheptan- 1 -al, and 2,5 ,S-trimethylhexan- 1 -al.
XIX
ethyl 3,6,9,9-tetramethyldeca-2,4-dienoate.
EXAMPLE 22 A. Eighty ml. of a 3M solution of methylmagnesium bromide in ether is added slowly to 31 g. of dihydrocitronellal in 250 ml. of dry ether. The mixture is heated at reflux for about 1 hour, cooled to 0 and treated with saturated aqueous ammonium chloride until reaction subsides. The organic layer is separated and the aqueous layer extracted with ether. The organic layer and ether extracts are combined, washed with water and brine and dried over magnesium sulfate. Evaporation of the solvent gives 4,8-dimethylnonan-2-ol.
B. A solution of 47 g. of 4,8-dimethylnonan-2-ol in 250 ml. of methylene chloride is cooled to about 10 as a solution of 46.4 g. of sodium dichromate in 125 ml. of water is added. The mixture is maintained at about 10 as a solution of 46.3 g. of sulfuric acid in ml.
of water is added over about 45 minutes. The mixture is allowed to attain room temperature and, after about 3 ,7,8-trimethylnonan- 1 -al, 2,4,5-trimethylhexan- 1 -al,
2,5-dimethylhexan- 1 -al, 3,5 ,6-trimethylheptan- 1 -al, 3 ,-dimethylheptan- 1 -al, 2,6-dimethylheptan- 1 -al and 2,5,6-trimethylheptan-l-al in place of dihydrocitronellal to yield the respective secondary alcohol 4,8-dimethyldecan-2-ol, 4methyl-8-ethyldecan-Z-ol, 4,8,8-trimethylnonan-2-ol, 4,8,8-trimethyldecan-2-ol, 4,7,8-trimethylnonan-2-ol, 4,8,9-trimethyldecan-2-ol, 3,5,6-trimethylheptan-2-ol, 3,6-dimethylheptan-2-ol,
4,6,7-trimethyloctan-2-ol,
4,7-dimethyloctan-2-ol, 3,7-dimethyloctan-2-ol, and 3,6,7-trimethyloctan-2-ol.
Each of the above alcohols is oxidized to prepare the respective ketone 4,8-dimethyldecan-2-one,
4-methyl8-ethyldecan-2-one,
4,8,8-trimethylnonan-2-one, 4,8',8-trimethyldecan-2-one,
4,7,8-trimethylnonan-2-one,
. 4,8,9-trimethyldecan-2-one,
3,5,o-trimethylheptan-2-one, 3,6-dimethylheptan-2-one,
, 4,6,7-trimethyloctan-2-one, 4,7-dimethyloctan-2-one, 3,7-dimethyloctan2-one, and 3,6,7-trimethyloctan-2-one.
C. Each of the ketones of part B is reacted withthe carbanion of diethyl 3-ethoxycarbonyl-2-methylprop- 2-enyl phosphonate according to procedures described above to prepare the respective 2,4-dienoate i.e.
ethyl 3,5,7,1 l-tetramethyldodeca-2,4-dienoate, ethyl 3,5 ,7,1 l-tetramethyltrideca-2,4-dienoate, ethyl 3,5 ,7-trimethyl-1 l-ethyltrideca-2,4-dienoate, ethyl 3,5,7,l l ,1 l-pentamethyldodeca-2,4-dienoate, ethyl 3,5,7,l l ,l 1-pentamethyltrideca-2,4-dienoate, ethyl 3 5 7 10,1 l-pentamethyldodeca-2,4-dienoate, ethyl 3,5,7 1 1,lZ-pentamethyltrideca-Z,4-dienoate, ethyl 3,5,6,8,9-pentamethyldeca-2,4-dienoate,
ethyl 3,5,6,9-tetramethyldeca-2,4-dienoate,
ethyl ,9,l0-pentamethylundeca-2,4-dienoate, ethyl 10-tetramethylundeca-2,4-dienoate, ethyl lO-tetramethyIundeca-2,4-dienoate, and ethyl ,9,10-pentamethylundeca-Z,4-dienoate.
EXAMPLE 23 A. Each of the ketones of part B of Example 22 is reacted with the carbanion of diethyl 3-ethoxycarbonyl- 1,2-dimethylprop-Z-enylphosphonate to prepare the respective 2,4-dienoate -i.e.,
ethyl 3 ,4,5 ,7, l l-pentamethyldodeca:2,4-dienoate,
ethyl 3,4,5,7,l l-pentamethyltrideca-2,4-dienoate,
ethyl 3,4,5,7-tetramethyl-l 1-ethyltrideca-2,4-
dienoate,
ethyl 3,4,5,7,1 1,1 l-hexamethyldodeca-2,4-dienoate,
ethyl 3,4,5,7,l l ,1 1-hexamethyltrideca-2,4-dienoate,
ethyl 3,4,5,7, l 0,1 l-hexamethyldodeca-2,4-dienoate,
ethyl 3,4,5 ,7, l l ,l2-hexamethyltrideca-2,4-dienoate,
ethyl 3,4,5,6,8,9-hexamethyldeca-2,4-dienoate,'
ethyl 3,4,5,6,9-pentamethyldeca-2,4-dienoate,
ethyl 3,4,5,7,9, lO-hexamethylundeca-2,4-dienoate,
ethyl 3,4,5,7, l O-pentamethylundeca-2,4-dienoate,
ethyl 3,4,5,6, lO-pentamethylundeca-2,4-dienoate,
. and
ethyl 3 ,4,5 ,6,9,10-hexamethylundeca-2,4-dienoate.
B. Each of the aldehydes under col. I is reacted with R is hydrogen and R is methyl or other lower alkyl.
Similarly, following the procedure of part A of this example, other ketones of formula I (R is lower alkyl) are converted into esters of formula B wherein each of R and R is lower alkyl. Using the process of part C of Example 22, other esters of the present invention of formula B wherein R is hydrogen and R is methyl or other lower alkyl can be prepared using a ketone of formula l (R is lower alkyl) as the precursor.
C. Each of the esters of this example and Example 22 can be hydrolyzed to the free acid according to the procedure of Example 5 or 20.
EXAMPLE 24 To a solution of 2 g. of methyl 3,7,1 1,1 l-tetramethyl- I trideca-2,4-dienoate and 20 ml. of dry ether, at -78,'
is added slowly 0.4 g. of lithium aluminum hydride in dry ether. The mixture is allowed to stand one hour and then is allowed to warm up to room temperature. Then about 2.5 ml. of acetic acid is added. The mixture is 3,8,12-trimethyltrideca-2,4-dien-l-ol,
3,8,1 3-trimethyltetradeca-2,4-dien- 1 -ol, and
3 ,7, l 3 trimethyltetradeca-2,4-dien- 1 ol.
Each of the esters listed below is reduced using lithium aluminum hydride to yield the respective allylic alcohol.
ethyl 3,7,1 1 ,l 1tetramethyldodeca-Z,4-dienoate,
methyl 3 ,7, l 0,1 1-tetramethyldodeca-2,4-dienoate,
methyl 3,6,8,9-tetramethyldeca-2,4-dienoate, methyl 3,7,9,10-tetramethylundeca-Z,4-dienoate, methyl 3,6, lO-trimethylundeca-Z,4-dienoate,
ethyl 3,5 ,7,1 l-tetramethyldodeca-2,4-dienoate,
ethyl 3 ,5 ,7, l 0, 1- 1 pentamethyldodeca-2,4-dienoate,
ethyl 3 ,5 ,7,9, l O-pentamethylundeca-Z,4-dienoate,
3 ,7 ,l 1,1 l-tetramemthyldodeca-2,4-dien- 1 -ol,
3 ,7, l 0,1 ltetramethyldodeca-2,4-dien- 1 ol,
3 ,6,8,9-tetramethyldeca-2,4-dien- 1 -ol,
3 ,7 ,9, l O-tetramethylundeca-Z,4-dien- 1 ol,
3,6,10-trimethylundeca-2,4-dien-1ol,
3 ,5,7, 1 ltetramethyldodeca-2,4-dien- 1 ol, 3 5 ,7, 10,1 1pentamethyldodeca-2,4-dien- 1 -ol, and 3 5 7 ,9, l O-pentamethylundeca-Z,4-dien- 1 ol.
EXAMPLE 25 To a mixture of 4 g. of 3,7,1 1,1 l-tetramethyltrideca- 2,4-dien-l-ol and 25 ml. of ether at 20 is added a solution of ml. of phosphorus tribromide in 18 ml. of ether over about minutes. The mixture is stirred at 0 for approximately one hour and then poured onto ice and extracted with pentane. The organic phase is washed with aqueous sodium bicarbonate, water and then brine, dried over magnesium sulfate and evaporated to yield l-bromo-3,7,ll,ll-tetramethyltrideca- 2,4-diene.
The process of this example is repeated using each of the alcohols of Example 24 to prepare the respective bromide, that is 3,7,1 1-trimethyldodeca-2,4-dienyl bromide,
3,7,1 ltrimethyltrideca-2,4-dienyl bromide,
3,1 1-dimethyl-7-ethyltrideca-2,4-dienyl bromide,
3,7,10-trimethylundeca-Z,4-dienyl bromide,
3,6,9-trimethyldeca-2,4-dienyl bromide, 3,6,9-trimethylundeca-2,4-dienyl bromide, 3,8 12-trimethyltrideca-2,4-dienyl bromide, 3 8 3trimethyltetradeca-2,4-dienyl bromide, 3 7 3-trimethyltetradeca-2,4-dienyl bromide, 3 ,7 l ,l ltetramethyldodeca-Z,4-dienyl bromide, 3,7 0,1 ltetramethyldodeca-2,4-dienyl bromide, 3 6 3 7 3 6 3 ,8,9-tetramethyldeca-2,4-dienyl bromide,
, ,9, l0-tetramethylundeca-2,4-dienyl bromide,
, ,lO-trimethylundeca-2,4-dienyl bromide,
,5 ,7,1 1-tetramethyldodeca-2,4-dienyl bromide, 3,5,7,10,1 1pentamethyldodeca-2,4-dienyl bromide,
and
3 ,5 ,7 ,9, 1 O-pentamethylundeca-2,4-dienyl bromide. By repeating the process of this example using phosphorus trichloride in place of phosphorus tribromide,
the novel allylic chlorides are prepared, e.g.
3,7,1 1 l 1-tetramethyltrideca-2,4-dienyl chloride, 3,7,1 ltrimethyldodeca-2,4-dienyl chloride, 3,7,1 1-trimethyltrideca-2,4-dienyl chloride, 3,7,10-trimethylundeca-2,4-dienyl chloride 3,6,9-trimethyldeca-2,4-dienyl chloride, 3,7,10,1 1tetramethyldodeca-2,4-dienyl and 3,5 ,7, 10,1 lpentamethyldodeca-Z,4-dienyl chloride.
chloride,
EXAMPLE 26 Ten grams of l-bromo-3,7,ll-trimethyldodeca-2,4- diene is mixed with 50 ml. of benzene, cooled to 5-10 and saturated with ammonia. The resulting mixture is stirred for 4 hours allowing the temperature to rise to about 20 while maintaining dry conditions. The mixture is washed with dilute sodium hydroxide and then evaporated under reduced pressure to yield 3,7,1 1- trimethyldodeca-2,4-dieny1amine.
EXAMPLE 27 Five grams of l-bromo-3,7,l l-trimethyldodeca-2,4- diene in 25 ml. of benzene is mixed with 4 g. of diethylamine and the mixture stirred for about 3 hours. Methylene chloride (50 ml.) is added and the mixture washed with dilute sodium hydroxide and then water and evaporated to yield N,N-diethyl 3,7,1l-trimethyldodeca-2,4-dienylamine.
. Although not intending to be limited by a theoretical fect, toxity effect or paralyzing effect, the compounds of this invention achieve control by reason of their ability to inhibit metamorphosis, inhibit reproduction due to abnormal development, break diapause'at an unfavorable time, or act as a direct insecticide, particularly at the embryo stage and larvae stage. Treatment of insects in accordance with the present invention can be achieved via ingestion of the active compound in the normal food of the insect and by topical application, that is, by contact of the epidermis of the insect as by spraying the insect and habitat of the insect or exposure to vapors of the active compound which penetrate into the insect.
The compounds of the present invention can be used in conjunction with other juvenile hormone active substances and conventional insecticides to obtainv a broader spectrum of activity or to provide more immediate effect on very heterogeneous populations. Typical insecticides which may be combined with the compounds of the present invention are Malathion, Sevin,
Vapona, synthetic and natural pyrethrins, and the like,
and usually within the ratio of between 10:1 to 1:10, by weight.
EXAMPLE 28 To a solution of 5.2 g. of 3,7,1 l-trimethyldodeca-2,4- dien-l-ol and 40 ml. of ether, cooled to 50, is added 2.45 g. of phosphorus tribromide in 5 ml. of ether over about 20 minutes. The reaction mixture is stirred for two hours, poured onto ice and extracted with ether. The ethereal extracts are combined, washed with 10% sodium carbonate, water and saturated sodium chloride, dried over sodium sulfate and solvent evaporated under reduced pressure to yield l-bromo-3,7,l l-trimethyldodeca-2,4-diene.
EXAMPLE 29 To 250 ml. of anhydrous pyridine, cooled in an icebath, is added 35.2 g. of p-toluenesulfonyl chloride. When the sulfonyl chloride is dissolved, 34 g. of 3,7,1 1- trimethyldodeca-2,4-dien-l-ol is added with 20 ml. of anhydrous pyridine. The reaction mixture is stirred at about 5-10 for 24 hours. Then 40 ml. of cold water is added and the mixture stirred for one hour at ice temperature. The mixture is extracted with pentane. The pentane extracts are washed with HC] and water, dried over potassium sulfate/potassium carbonate and concentrated under reduced pressure. The concentrate is taken up in 50 ml. of dry acetone and added to a solution of 36 g. of dry sodium iodide in 150 m1. of dry acetone. The reaction mixture is stirred at room temperature for about 20 hours and then filtered. The filtrate is concentrated and taken up in pentane. The pentane solution is washed with water, dried over sodium sulfate and evaporated to yield 3,7,1l-trimethyldodeca-2,4-dienyl iodide, which can be purified by chromatography.
EXAMPLE 30 A mixture of 33 g. of l-bromo-3,7,l l-trimethyldodeca-2-,4-diene and 100 ml. of dry ethylene glycol in slowly added, with stirring, to a suspension of 11.5 g.
of potassium fluoride in 30 ml. of dry ethylene glycol and heated to about under an inert atmosphere. When addition is completed, the reaction mixture is stirred for about an additional 16 hours while maintaining the temperature at 120. Then the mixture is cooled and 200 ml. of ether added. The mixture is washed thoroughly with water and the ether phase dried over sodium sulfate and solvent evaporated under reduced pressure to yield l-fluoro-3,7,l l-trimethyldodeca-2,4- diene.
The same compound can be prepared by using an equivalent amount of silver fluoride in place of potassium fluoride.
What is claimed is:
l. A compound of the formula:
CH3 on; CH3 HR-0H2oH.cH2o -bHoH2oH=oH-b=oHoHQ-X I 3,7,1 l-trimethyldodeca-2.,4- dienyl chloride.
3,7,1 l-trimethyldodeca-2,4- v

Claims (3)

1. A COMPOUND OF THE FORMULA:
2. The compound, 3,7,11-trimethyldodeca-2,4-dienyl bromide.
3. The compound, 3,7,11-trimethyldodeca-2,4-dienyl chloride.
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4054605A (en) * 1975-04-17 1977-10-18 Texaco Development Corporation Unsaturated amino alcohols
US4072725A (en) * 1975-10-16 1978-02-07 Scm Corporation Dehydrophytol
USRE29829E (en) * 1974-05-16 1978-11-07 Scm Corporation Insect repellent compositions and process having an N-substituted hydroxyalkyl amine as an active ingredient
EP0003361A1 (en) * 1978-02-01 1979-08-08 BASF Aktiengesellschaft 3,5,5-Trimethylhexane-1-ols and their esters, their syntheses and their application as odorants
US4357471A (en) * 1976-12-17 1982-11-02 Rohm And Haas Company Azaspiro compounds
US4374991A (en) * 1976-12-17 1983-02-22 Rohm And Haas Company 2,6-Dimethylpiperidinyl-N-carbobutoxymethyl urea
US4400512A (en) * 1976-12-17 1983-08-23 Rohm And Haas Company Azaspiro compounds
US4405630A (en) * 1980-12-29 1983-09-20 Rohm And Haas Company Arthropod repellent compositions and methods

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Publication number Priority date Publication date Assignee Title
US3706733A (en) * 1971-02-16 1972-12-19 Clive A Henrick Epithio-thiol-dienoates

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3706733A (en) * 1971-02-16 1972-12-19 Clive A Henrick Epithio-thiol-dienoates

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE29829E (en) * 1974-05-16 1978-11-07 Scm Corporation Insect repellent compositions and process having an N-substituted hydroxyalkyl amine as an active ingredient
US4054605A (en) * 1975-04-17 1977-10-18 Texaco Development Corporation Unsaturated amino alcohols
US4072725A (en) * 1975-10-16 1978-02-07 Scm Corporation Dehydrophytol
US4357471A (en) * 1976-12-17 1982-11-02 Rohm And Haas Company Azaspiro compounds
US4374991A (en) * 1976-12-17 1983-02-22 Rohm And Haas Company 2,6-Dimethylpiperidinyl-N-carbobutoxymethyl urea
US4400512A (en) * 1976-12-17 1983-08-23 Rohm And Haas Company Azaspiro compounds
EP0003361A1 (en) * 1978-02-01 1979-08-08 BASF Aktiengesellschaft 3,5,5-Trimethylhexane-1-ols and their esters, their syntheses and their application as odorants
US4405630A (en) * 1980-12-29 1983-09-20 Rohm And Haas Company Arthropod repellent compositions and methods

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