US3296321A - Cyclic acetylenic hydrocarbon preparation - Google Patents

Cyclic acetylenic hydrocarbon preparation Download PDF

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US3296321A
US3296321A US432034A US43203464A US3296321A US 3296321 A US3296321 A US 3296321A US 432034 A US432034 A US 432034A US 43203464 A US43203464 A US 43203464A US 3296321 A US3296321 A US 3296321A
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reaction
compounds
cyclic
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Bobby F Adams
John H Wotiz
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Diamond Shamrock Corp
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Diamond Alkali Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/325—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
    • C07C1/325—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom
    • C07C1/328—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom the hetero-atom being an alkali metal atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C11/00—Aliphatic unsaturated hydrocarbons
    • C07C11/22—Aliphatic unsaturated hydrocarbons containing carbon-to-carbon triple bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered

Definitions

  • the present invention comprises the process illustrated by the following equation and certain novel products thereof:
  • M M M and M are the same or difierent substituted alkylene radicals, e.g'., and are selected from the group consisting of copper, oalkl H alkali metals, i.e..
  • a is a number from 0 to 20, inclusive; b is a number from O to 2, inclusive; 0 is a number from 0 to 20, inclusive; with the proviso that when b is 0 or 1, either a or c is equal to or greater than 3 or the sum of a and c is equal to or greater than 3; d is a number from 0 to 20, inclusive; e is a number from 0 to 20, inclusive; 1 is a number from 0 to 2, inclusive; with the proviso that when f is 0, the sum of e and g is equal to or greater than 3; g is a number from 0 to 20, inclusive; y is a number from 1 to 10,000; X is chlorine, bromine, iodine or tosyl radical R and R are the same or different radicals selected
  • a preferred linear polyyne of this invention' has the structure:
  • Z is an alkalene radical
  • h is a number from 3 to 10, inclusive
  • i is a number from 2 to 10, inclusive.
  • alkylene radical as employed in the specification and claims, unless otherwise defined,- is intended to refer broadly to organic hydrocarbon radicals having the general formula C H m being a number from 1 to about 50, inclusive, e.g., 1 to 20, which radicals may be either straight chain or branched chain, e.g., those having 2 to carbon atoms.
  • preferred lower molecular weight hydrogen-ended alpha, omega polyacetylenic hydrocarbons e.g., alpha, omega triacetylenic and alpha, omega kylene radicals are those containing 5 carbon atoms, e.g.:
  • tetraacetylenic hydrocarbons of this invention may be represented by the structure:
  • R and R are alkylene radicals containing from 2 to about 15 carbon atoms, e.g., polymethylene and branched chain polymethylene radicals, such as ethylene, trimethylene, tetramethylene, pentamethylene, heptamethylene, propylene, butylene, and the like.
  • Novel alpha, omega triacetylenic hydrocarbons of this invention may be represented by the structure:
  • linear compounds of this invention are alpha, omega tetraacetylenic hydrocarbons which may be represented by the structure:
  • R R and R are alkylene radicals containing from 2 to about 50 carbon atoms, inclusive.
  • Specific i1- lustrative tetraacetylenic hydrocarbons within structure VII are:
  • n is a number equal to or greater than 1, e.g., a number from 1 to about 15, R and R are alkylene radicals containing at least 5 carbon atoms, and x is a number from 1 to 20, inclusive.
  • R and R are alkylene radicals having at least 5 carbon atoms, e.g., 5 to 50 carbonatoms.
  • Specific illustrative cyclic acetylenic hydrocarbons within the scope of the structure IX are:
  • Polyynes of this invention can also be prepared using a polyacetylide as a reactant (I), e.g., mm) 01mm X(CH2),X M-ozo orn ,o0- ⁇ CE/g
  • a reactant e.g., mm
  • Compound XI is employedas a reactant when it is desired to minimize the formation of high molecular l weight products; when it is omitted, a polymeric product [J XIII and XIV are formed.
  • Appropriate ll'gixtures of XI '1 and XII can be prepared by metering a nown v0 ume H (0119 of acetylene in to a suspension of NaNH (from weighed L l amount of Na) in liquid NI-I e.g.
  • a high concentra- -CEC is intended to refer to compounds which i f N cb f C f Produce the linkage in the reaction Y vors the formation of cyclic product, whereas a high con-
  • the preferred compounds of this type are dicentrationof NaCEC-H (absence of alkali metal acetylides, such as disodium, dilithiurn and/ or dipotassium acetylides, the expression is not to be so favor r r d t If N H t limited since it is intended to refer broadly to mono th S S 1 6;: 3 prism and polyacetylide compounds providing the desired pro b 7 2 g d 0 mear CEC- linkage, e.g., alkaline earth acetylides such r p yyne e orme owever Secon ary reac' as calcium, barium, str
  • the yield of cyclic product increases with an increase in dilution.
  • the same quantity of reactants in one liter of solvent e.g., NH will yield less cyclic product than the corresponding reaction in liters of solvent.
  • cyclic product will also depend on the value of n in X(CH ),,X. Specifically, we find that intramolecular reaction is the favored reaction when 11:5.
  • the product 1,8-cyclotetradecadiyne is formed in relatively high yield even'over a wide range of mono to disodium acetylide ratios.
  • a linear product is favored in concentrated solutions, absence (or low concentration) of chain stoppers (e.g. NaCECI-I) and with molecules Where reactive ends are not likely to self-condense.
  • the dialkali metal acetylide may be prepared by any convenient method; for example, the following empirical equations illustrate several other methods for the preparation of this compound, any one of these preparations being satisfactory.
  • the polyynes of this invention may be prepared by chemically reacting separately prepared dialkali metal acetylide and an alkylene dihalide or they may be prepared in situ with the initial preparation of the disodium acetylide, i.e., sodium and acetylene may be reacted in the presence of ammonia followed by the addition of the alkylene dihalide, preferably in the same reaction zone.
  • a desired ratio mono to disodium acetylide can be established by adjusting the amount of acetylene that is introduced into a reaction vessel containing a given amount of NaNH e.g.,
  • the disodium acetylide may be prepared in a reaction zone separate from the reaction zone in which the disodium acetylide is reacted with the alkylene dihalide.
  • exemplary of this is the preparation of compounds wherein 2 moles of the disodium acetylide previously prepared in a separate reaction zone are reacted with l to 3 moles of the alkylene dihalide.
  • This reaction is typically and advantageously carried out in a polar solvent such as anhydrous liquid ammonia; other solvents which may be employed are butylamine, ethylenediamine, triethylamine, tetrahydrofuran, dimethylether of diethylene glycol, dimethylether, dimethylformamide, dimethylacetamide, methyl pyrolidone, ethyl acetal, and dioxane or mixtures of the foregoing, e.g., a mixture of dimethylformamide and tetrahydrofuran.
  • solvents also may be diluted with neutral solvents such as ethyl ether or other aliphatic or aromatic solvents.
  • the reaction temperature generally is dictated by the solvent employed, e.g., reaction is typically carried out at the reflux temperature of the solvent or solvent mixture; a temperature of 30 to -35 C is typical when employing liquid ammonia. to 200 C. may be used. If necessary, superatmospheric pressures of up to about 40 atmospheres are generally satisfactory; if desired, higher pressures also can be used.
  • the reaction occurs in a period of about 1 to 48 hours, typically 1 to 24 hours, the exact reaction time depending on a number of factors, e.g., solvent, reactivity of halide (I Br Cl) and especially temperature.
  • the desired polyacetylenic hydrocarbons can be isolated upon reaction completion by adding water or other proton donor solvents, e.g., alcohols such as methanol, ethanol,
  • amine, tetrahydrofuran, and ethers such as dimethylether, diethylether, dimethylether of diethylene glycol and dimethylformamide dioxane, mixtures of the foregoing, ,or any of the polar solvents previously referred to herein, e.g., a mixture of dimethylformamide and tetrahydrofuran may be employed'
  • the reactants are mixed in the order indicated in the above equations at a temperature dictated 'by the solvent employed, but typically at a temperature of about 100 C. to 200 C., e.g., 35 C. to +25" C.
  • an equivalent excess of the acetylide reactant is employed; also, an excess of NH when employed as solvent may be desirable.
  • the reaction is typically carried to completion over a period of about 3 to 36 hours.
  • Isolation of the product may be carried out by means common in the art, such as recrystallization from an organic solvent, e.g., petroleum ether, methanol, diethyl ether, benzene, ethanol, propanol and the like; the desired product may also be isolated through distillation typically at reduced pressure or through either liquid or vapor phase chromatography,
  • compositions VI and VII Specific illustrative preparations involving the reaction of disodium acetylide and an alkylene dihalide are the preparation of compounds of structures VI and VII above.
  • the preferred preparation of these compounds VI and VII comprises chemically reacting disodium acetylide and an alkylene dihalide, the disodium acetylide 'being prepared in the same reaction zone, these reactants may be prepared and combined in separate reaction zones, i.e., the disodium acetylide may be prepared in a reaction zone separate from that employed in the reaction of di- However, temperatures of 9 sodium acetylide, and the alkylene dihalide.
  • Typical reaction conditions in the preparation of alpha, omega triand tetraacetylenic hydrocarbons are as follows: 2000 to 5000 parts by weight of liquid ammonia is mixed with l to parts -by weight of a catalyst, e.g., ferric nitrate, iron oxide, or sodium peroxide; followed by the addition of 50 to 100 parts by weight of sodium metal to form sodium amide; 50 to 100 parts by weight of acetylene gas is then added to this mixture. 2 to 4 moles of an alkylene dihalide is added at a rate sufficient to maintain a gentle refluxing of the ammonia. Upon reaction completion, 100 to 2000 parts by weight of water are added slowly to the reactant mixture with agitation.
  • a catalyst e.g., ferric nitrate, iron oxide, or sodium peroxide
  • the desired product is isolated by recrystallization from an organic solvent, such as petroleum ether, methanol, ethanol, propanol, diethyl ether or benzene, the resultant product being further distilled at reduced pressure yielding the desired triand tetraacetylenically unsaturated compounds.
  • an organic solvent such as petroleum ether, methanol, ethanol, propanol, diethyl ether or benzene
  • this cyclic hydrocarbon is enhanced by increased dilution of the initial starting materials, typical proportions being about 4000 to 8000 parts by weight of solvent, 70 to parts by weight disodium acetylide, and 1 to 2 moles of alkylene dihalide.
  • the specifically preferred preparation at present is the reaction of disodium acetylide, prepared either in the same reaction zone or in a diiferent reaction zone, with a polymethylene dibromide, this reaction taking place in the presence of a solvent, typically liquid ammonia, under the same reaction conditions given previously.
  • a solvent typically liquid ammonia
  • Fractional vacuum distillation is used if the boiling points are below the decomposition temperatures. Pot temperatures up to 350 C. are used.
  • Fractional crystallization from conventional solvents, e. g., petroleum ether, can be used in cases where the products have close boiling points, e.g.,
  • this invention exhibit activity as insecticides, fungicides,
  • While compounds of this invention may be employed in a variety of applications, biologically active or otherwise, when employed as biologically active materi-als it will be understood, of course, that such compounds may be utilized in diverse formulations both liquid and solid including finely-divided powders and granular materials as well as liquids such as solution, concentrates, emulsifia ble concentrates, slurries and the like, depending upon the application intended and the formulation media desired.
  • These compounds may be used alone or in combination with other known biologically active materials such as other acetylenically unsaturated compounds, organic phosphate pesticides, chlorinated hydrocarbon insecticides, foliage and soil fungicides, and the like.
  • compositions may also include finelydivided dry or liquid carriers, extenders, fillers, conditioners, including various clays, suchastalc, spent catalyst, alumina silica materials, liquids, solvents, diluents or the like, including water and various organic liquids such as benzene, toluene, chlorinated benzene, acetone, cyclohexanone, chlorinated xylene, carbon tetrachloride, ethylene dichloride, tetrachloroethylene, carbon disulfide, and alcohols at various temperatures'thereof.
  • finelydivided dry or liquid carriers extenders, fillers, conditioners, including various clays, suchastalc, spent catalyst, alumina silica materials, liquids, solvents, diluents or the like, including water and various organic liquids such as benzene, toluene, chlorinated benzene, acetone, cyclohexanone, chlorinated xylene,
  • liquid formulations When liquid formulations are employed or dry materials prepared which are to be used in liquid form, it isvdesirable in certain instances additionally to employ a wetting, emulsifying or dispersing agent to facilitate use of the formulation, e.g., Triton X-155 (alkyl aryl polyether alcohol, US. Patent 2,504,064).
  • a wetting, emulsifying or dispersing agent e.g., Triton X-155 (alkyl aryl polyether alcohol, US. Patent 2,504,064).
  • Triton X-155 alkyl aryl polyether alcohol, US. Patent 2,504,064
  • Other suitable surface active agents may be found in an article by John W. McCutcheon in Soap and Chemical Specialties, vol. 4, Nos. 7-10 (1955).
  • carrier as employed in the specification and claims is intended to refer broadly to materials constituting a major proportion of a biologically active or other formulation and hence, includes finely-divided materials both liquids and solids, as aforementioned conveniently used in such applications.
  • the present invention relates to pesticidal compositions containing the acetylenic hydrocarbons of this invention, e.g., 1,7,l3,19,25-hexacosapentayne as a contact poison for bean beetles, and to methods of killing pests employing these compositions.
  • the compounds of this invention are useful in the inhibition of decomposition of a halogenated aromatic hydrocanbon.
  • a halogenated hydrocarbon e.g., a chlorinated xylene
  • n is a number equal to or greater than 1, e.g., a number from 1 to about 15, inclusive
  • R and R are alkylene radicals having greater than 4 carbon atoms, e.g., 1,8,15-hexadecatriyne. It has also been found that compounds within the scope of structure VIII are particularly useful in the stabilization of benzyl chloride,,the preferred compound in this application being 1,8-cyclotetradecadiyne.
  • a chlorinated xylene in a pure condition may be stored or shipped with little or no decomposition induced by exposure to air, light, heat and/or moisture.
  • xylenes normally encountered in commerce are subject to some degree of decomposition when in contact with substances such as specks of rust or aluminum, dirt, air, light, heat, moisture and the like.
  • means for preventing and/or inhibiting this decomposition of chlorinated xylenes and/or other chlorinated aromatic hydrocarbons generally associated therewith are highly desirable.
  • aliphatic hydrocarbons as perchlorethylene but are ineffective for the stabilization of chlorinated xylenes such as alpha-chloro-p-xylenes in that significant decomposition occurs even though the alpha-chloro-pxylene contains relatively large quantities of these compounds.
  • Monoacetylenic monoolefinic hydrocarbons and straight chain acetylenic esters are unsatisfactory for the same reason.
  • compositions employed in the stabilization of chlorinated xylenes and the method of statibilizing such compounds are highly selective, and, therefore, those stabilizers employed previously in the stabilization of chlorinated aliphatic hydrocarbons, such as carbon tetrachloride, perchlorethylene, tetra chlorethylene and the like, are not adaptable to the stabili- Unstabilized quantities of halogenated aromatic hydrocarbons as produced, including such compounds as alphachloro-p-xylene and benzyl chloride, may be either in a relatively pure or impure condition.
  • halogenated aromatic hydrocarbon depends uponits age, i.e., the length of time it has stood unstabilized after production without particular eiforts being made to prevent the decomposition. Accordingly, a relatively impure halo aromatic hydrocarbon is found to be of limited utility for many industrial needs although further decomposition may -be inhi bted by using ,the stabilizers for the present invention. On the other hand, some unstabilized halo'aromatic hydrocarbons are employed while relatively fresh and are correspondingly pure and usable. Such materials require only stabilization against further decomposition in order to be satisfactory for a number of uses.
  • the chlorinated aromatic hydrocarbon may. require pretreatment of .a nature such that the major proportion or substantially all of the impurities are removed prior to the addition of stabilizers so as to provide a material having a good initial level of acceptability for industrial needs.
  • some chlorinated aromatic hydrocanbons may not require such pretreatment although those skilled in the art will understand that a chlorinated xylene containing undesirable impurities may advantageously be treated for the removal or reduction of any impurities prior to stabilization.
  • Such purifications may be effected through means common in the art, such as distillation.
  • the present invention is directed to a composItion comprising essentially a chlorinated aromatic hydrocarbon, e.g. a normally liquid chlorinated xylene, such as alpha-chloro-p-xylene and a stabilizing amount of at least one polyacetylenic hydrocarbon, i.e., triacetylenic hydrocarbon and tetraacetylenic hydrocarbon, preferably 1,8,15-hexadecatriyne.
  • a chlorinated aromatic hydrocarbon e.g. a normally liquid chlorinated xylene, such as alpha-chloro-p-xylene
  • a stabilizing amount of at least one polyacetylenic hydrocarbon i.e., triacetylenic hydrocarbon and tetraacetylenic hydrocarbon, preferably 1,8,15-hexadecatriyne.
  • the present invention is directed to a composition
  • a composition comprising essentially benzyl chloride and a stabilizing amount of at least one cyclic acetylenic hydrocarbon, e.g., 1,8-cyclotetradecadiyne.
  • the invention is directed to such a composition including an additional ingredient efiective to exert a stabilizing action againt the influence of light and other sources of decomposition.
  • This is intended to include other stabilizers which may be combined with the stabilizers of the present invention which cause a synergistic effect concerning the stabilization of halogenated aromatic hydrocarbons.
  • a new class of stabilizers noted above namely, alpha, omega, triand tetraacetylenic hydrocarbons have been found particularly effective in stabilizing alpha-chloro-p-xylene contaminated with minor amounts of metallic ions, such as those produced by specks of rust or aluminum, both in a liquid or in a vapor phase.
  • metallic ions such as those produced by specks of rust or aluminum
  • the stabilizing effect has been found to be most pronounced and prolonged where pretreatment which removes the greater part of contaminating metallic ions has been resorted to prior to the addition of the stabilizing alpha, omega, trior tetraacetylenic hydrocarbon.
  • the method of stabilizing halogenated aromatic hydrocarbons comprises essentially contacting a major proportion of the halogenated aromatic hydrocarbons, i.e., the chlorinated xylenes or benzyl chloride, with a stabilizing amount of the alpha, omega polyacetylenic hydrocarbon or the polycycloacetylenic hydrocarbon, respectively.
  • the stabilizer be added after the initial preparation of the halogenated hydrocarbon, i.e., after the chlorination step, and that the stabilizing amount of the respective stabilizers be combined, as noted above e.g., in an amount of about 0.0001% to by weight of the halogenated aromatic hydrocarbon, preferably, however, from about 0.1% to 1% by weight of the chlorinated aromatic hydrocarbon. Under more adverse conditions, such as higher temperatures and/or excessive contamination, it may be necessary to add several percent of the stabilizer. Large quantities of the stabilizer are seldom necessary or desirable and in most cases amounts of stabilizer less than 5% by weight of the halogenated aromatic hydrocarbon protect the halogenated compound against the decomposition under the most severe conditions normally encountered.
  • the indicated intermediate preferred range is generally sufficiently effective for the purified halogenated aromatic hydrocarbon containing not more than 0.2% by weight of the metallic impurities most common in commercial production.
  • compounds of this invention include polymers, solid rocket fuel binders, coatings, films, fibers, intermediates, polymerization catalysts, high energy fuels, rocket fuel starters,'plasticizers, stabilizers, and the like.
  • Example 1-Preparation 0f 1,8-cyclotetradecadiyne 2.5 liters of liquid ammonia is placed in a flask, followed by the addition of 1.35 g. of ferric nitrate hydrate (0.3 g. for each g. atom of sodium employed). 2.0 g. of sodium metal is then added and activated by bubbling dry air into the mixture. 103.5 g. (4.4 mol) of sodium metal is added in small portions and 54.3 liters (2.2 mol) of acetylene gas at 28 C. and 747 mm. mercury pressure is bubbled into the suspension of the sodium amide and 500 g.
  • the resultant gummy solid is found to be soluble in organic solvents, i.e., pentane and ether.
  • Isolation of the desired acetylenic cyclic hydrocarbon is accomplished by recrystallization from ether, yielding not only the cyclic hydrocarbon but also the respective triand tetraacetylenically unsaturated compounds as by-products.
  • the crude product is further vacuum distilled and recrystallized from ether, yielding the desired product melting at 99 to 100 C.
  • This C H having a molecular weight of 188.3, is indicated by the following elemental analytical data:
  • Example 2 The procedure given in Example 1 is carried out separating the 1,8,15hexadecatriyne distilling at to C. at .7 to 1.0 mm. mercury pressure.
  • This triacetylenic hydrocarbon has a refractive index at 25 C. of n 1.4774, this O l-I being indicated by the following elemental analytical data:
  • Example 3 Preparation of 1,7,I3-telradecatriyne and and 1,7,]3,19-eic0satelrayne eicosatetrayne-S 15 evolved the stirrer is speeded up to wash the flask walls free of spattered sodium. Acetylene is then added to the mixture until the milky suspension begins to clear, typically about /2 to 2 hours. 648 g. (3.0 mol) of tetramethylene dibromide is then added at a rate to retain a gentle reflux of liquid ammonia. Upon reaction completion, the ammonia is allowed to evaporate. About 200 to 300 mls. of water is then added with caution and the two layers formed, i.e., the organic layer and aqueous layer, are extracted several times with 100 ml. portions of ether.
  • Example 4 To further demonstrate insecticidal activity of 1,7,13,- 19-eicosatetrayne, fourth instar larvae of the Mexican bean beetle, Epilachna varivestis, less than one day old within the instar, are employed. Paired seed leaves, excised from Tender-green bean plants, are dipped in a formulation of the test chemical (2000 p.p.m. 1,7,13,19-
  • Example 6 In order to evaluate insecticidal activity of the compounds of this invention, male German cockroaches, Blattella germanica, 8 to 9 weeks old, are anaesthetized with carbon dioxide to facilitate handling and then dipped in a test formulation (2000 ppm. test chemical% 16 acetone0.0l% Triton Xl55balance water) for 10 seconds, removed and freed of excess liquid, and caged. Two lots of 10 insects each are exposed to this formulation and mortality observations are recorded after three days. Using this procedure, the following mortality ratings are observed:
  • Example 7 Insecticidal utility of 1,7,l3,l9-eicosatetrayne, i.e., one of the products of Example 3, is shown in the following test.
  • the bean aphid, Aphis fabae is cultured on nasturtium plants. No attempt is made to select insects of a given age in this test.
  • Test pots are prepared by reducing the number of nasturtium plants in 2 /2 inch culture pots until those remaining are infested with approximately 100 aphids.
  • the infested test plants are treated with a formulation of the test chemical (2000 p.p.m. 1,7,13,19 eicosatetrayne-5% acetone0.01% Triton X155balance water) Based on counts made 24 hours after exposure greater than mortality is observed.
  • Example 9 Spore germination tests on glass slides are conducted via the test tube dilution method adapted from the procedure recommended by the American Phytopathological Societys committee on standardization of fungicidal tests.
  • the product of Example 2 in aqueous formulations at concentrations of 1000, 100, .10 and 1.0 p.p.m. is tested for its ability to inhibit germination of spores from 7 to 10 day old cultures of Alternaria oleracea and Monilinia fructicola.
  • concentrations refer to initial concentrations before diluting four volumes with one volume of spore stimulant. and spore suspension.
  • Germination records taken after 20 hours of incubation at 22 C. by counting spores. Based on a rating system whereby thelisted concentration afi'ords disease control,
  • Example A tomato foliage disease test is conducted measuring the ability of the product of Example 2 to protect tomato foliage against infection by the early blight fungus Alternaria solani. Tomato plants 5 to 7 inches high of the variety Bonny Best are employed. The plants are sprayed with 100 ml. of test formulation at 2000 p.p.m. (2000 p.p.m. product of Example 25 acetone0.01% Triton X-155balance water) at 40 lbs. air pressure while being rotated on a turntable in a spray chamber. After the spray deposit is dry, the treated plants and comparable untreated controls are sprayed with a spore suspension containing approximately 20,000 conidia of A. solam' per ml.
  • the plants are held in a 100% humid atmosphere for 24 hours at 70 F. to permit spore germination and infection. After 2 to 4 days, lesion counts are made on the three uppermost fully expanded leaves. Data based on the number of lesions obtained on the control plants shows better than 75% disease control.
  • Example 11 To evaluate bactericidal activity, the test chemical is mixed with distilled water containing 5% acetone and 0.01% Triton X-l55, at a concentration of 250 p.p.m. 5 ml. of the test formulation are put in each of four test tubes. To each test tube is added one of the organisms: Erwenia amylovora, Xanthomonas phaseoli, Staphylococcus aureus and Escherichia coli in the form of a bacterial suspension in a saline solution from potato-dextrose agar plates. The tubes are then incubated for 4 hours at 30 C. Transfers are then made to sterile broth with a standard 4 mm. loop and the thus-innoculated broth is incubated for 48 hours at 37 C. Using this procedure the products of Example 3 afford the noted bacterial control:
  • 1,7,13-tetradecatriyne 100-1, 000 100-1, 000 1,7,13,19-eicosatetrayne 1, 000 1001, 000
  • Example 13 To evaluate the effect of the compounds of this invention upon the germination of seeds in soil, a mixture of seed of six crop plants is broadcast in 8 x 8 x 2 inch metal cake pans filled to within /2 inch of the top with composted greenhouse soil. The seed is uniformly covered with eter x 8 mm. deep),
  • Example 1 receives ratings of 2, '3, 11 and l for the tomato, bean, corn and oat plants, respectively, thus demonstrating selective herbicidal activity.
  • Example 15 In order to demonstrate the effectiveness of a stabilizer of the present invention, a procedure is carried out by which alpha-chloro-p-xylene is stabilized with 1,8,15-hexadecatriyne.
  • 25 ml. of alpha-chloro-pxylene is placed in each of six 4 ounce clear glass containers.
  • 1,8,15-hexadecatriyne is added to the first five containers in concentrations of 0.0125 g., .025 g., .125 g., .250 g., and .500 g., respectively.
  • a metal contaminant comprising 50% iron powder and 50% iron oxide is then added in concentrations of from 0.01 g. to 0.5 g. per container.
  • Example 17 To further demonstrate the effectiveness of a combination of stabilizers of the present invention, a procedure is carried out by which alpha-chloro-p-xylene is stabilized with 1,8,15-hexadecatriyne and ethylene glycol.
  • 25 ml. of the alpha-chloro-p-xylene is placed in each of four 4-ounce clear glass containers.
  • a combination of 0.0125 g. of 1,8,15-hexadecatriyne and 0.0125 g. of ethylene glycol is added to the first container.
  • To the second To the second a combination of 0.0625 g. of the triyne and 0.0625 g. of ethylene glycol is added and a combination of 0.125 g.
  • Example 18 A further demonstration of the effectiveness of the ception that a concentration of .0625 g. of the triyne in combination with .0625 g. of the alpha, omega diacetylenic ester is employed. This test indicates that at this concentration, the combination of the alpha, omega polyacetylenic hydrocarbon and the alpha, omega diacetylenic esters are efiective as stabilizers for alpha-.
  • chloro-p-xylene for a period of at least three days.
  • Example 19 Stabilizing eifectiveness of the product of Example 1 is demonstrated by stabilizing benzyl chloride employing essentially the same test procedure given in Example 16. In this test the cyclic compound is completely ineffective in stabilizing alpha-chloro-p-xylene, but all the solutions.
  • benzyl chloride are colorless after a period of greater than 15 days.
  • Example 20 Preparation and alkylation of sodium acetylides Sodium (7 mol) is reacted with 4 liters of anhydrous ammonia at 33 in the presence of iron containing.
  • the products are characterized by petroleum ether.
  • stabilizers of the present invention is carried out by sta- Q boiling and melting points, index of refraction and in: bilizing alpha-chloro-p-xylene with a combination of 1,8, frared spectra.
  • Sodium amide is prepared from 69 g. (3.0 mol) of sodium and 3 liters of anhydrous ammonia, at its boiling point (-32), and in the presence of iron containing catalyst.
  • a 2: 1 mixture of N2.CECH to NaCECNa is then prepared by the introduction of 2.25 moles of acetylene (measured with the aid of a wet test .gas meter).
  • the addition of 382 g. (1.0 mol) of I(CH O(CH I is over a period of 4 hours.
  • the stirred mixture is kept near 32 While ammonia is permitted to evaporate through a cellophane-capped outlet.
  • the residue is diluted with water and the organic layer washed with dilute HCl, and dried. Repeated fractional distillation yields:
  • the 5-hexynyl ether exhibits activity as a contact poison against roaches, as a systemic rust fungicide and as a bactericide.
  • Example 23.Prepara1tion of H--CEc(CH )5CEC(C H CEC(CH 5CECH Sodium amide is prepared from 23 g. (1.0 mol) of sodium and 2 liters of liquid ammonia at 32. To this suspension is added 211 g. (1.75 mol) of HCEC(CHZ) CECH" The product is alkylated with 69 g. (0.3 mol) of BY(CH2)5BI The suspension is stirred for 16 hours while ammonia is permitted to evaporate through a. cellophane-capped opening. The residue is diluted with water and the organic layer washed with dilute HCl and dried. Distillation results in the recovery of 144 g.
  • Example 24 E-Prepdration of Sodium amide is prepared from '51 g. (2.2 mol) of sodium and 3 liters of liquid ammonia (32"). To this suspension is added 116 g. (1.1 mol) of and the product is alkylated with 216 g. (1.0 mol) of Br(CH Br. The mixture is stirred for 16 hours while ammonia is permitted to evaporate through a cellophanecapped opening. The residue is diluted with water and the organic layer washed with dilute HCl and dried. Distillation results in a recovery of 15 g. of the starting 1,7-octadiyne and 8.0 g. of 1,7-cyclododecadiyne, M.P. 389.
  • Example 25 Preparation of /CEC H2)s ozo Sodium amide is prepared from 46 g. (2.0 mol) of sodium and 2 liters of liquid ammonia (-32). To this mixture is added 120 g. (1.0 mol) of and the product is alkyla-ted with 173 g. (0.8 mol) of Br(CH Br. The suspension is stirred and the ammonia permitted to evaporate through a cellophane-capped opening for 16 hours. The residue is diluted with water and the organic layer washed with dilute HCl and dried. Distillation yields 42 g. of 1,7-cyclotridecadiyne, B.P. 83-4 at 0.08 mm., M.P. 7, n 1.5060.
  • Example 27 -Preparation of H-CEC(CH2)3CEC(CH2)3CEC(CH2)3CEC-H (2.) N11, 3 liters; NaNH- 2 moles from 46 g. (2 M) of Na (e) Br(CH Br, 161 g. (0.8 mole)
  • Example 28. Preparatian of HCEC(CH CEC(CH ,-CEC(CH CECH (a) NH 3 liters; NaNH 2 moles from 46 g. (2 M) (b I- I CEC(CH CECH, 536g. (4 moles) (c) Br(CH Br, 195 g.
  • Example 35 A suspension of 192 g. (4 moles) of monosodium acetylide (NaC CH) in 2 liters of kerosene (mixture of satu- I rated hydrocarbons) is stirred and heated at 200.until 22.4 liters (STP) of acetylene is evolved. The suspension is cooled to 25 and the agitation stopped to permit the 1 solids to settle. The kerosene is sucked oil and the solids washed in succession with three 200 ml. portions of petroleum ether, and stored as slurry in petroleum ether.
  • NaC CH monosodium acetylide
  • STP 22.4 liters
  • Example 36 A 5-1iter three-necked flask is fitted with a reflux con denser, stirrer and gas inlet tube.
  • a sodium dispersion IO-25 microns particle size, containing 0.25% of aluminum stearate and 0.5% of 1 oleic acid
  • xylene xylene
  • Purified acetylene passesed through 90% H and a column. filled with activated alumina
  • sur-: 1 face of the suspension A total of 78.4 liters (STP, 3.5
  • Example 37 Four moles (dry basis) of KOH pellets and 3 moles (active ingredient basis) of commercial calcium carbide are slurried in 1.5 liters of butyl carbitol at 150 C. for three hours. Low boiling liquids, mainly water, are permitted to distill out of the reaction flask. The reaction product is cooled to 50 C. while vigorously stirred. Such a suspension can be used immediately in reactions with dihalides.
  • Example 38 Four moles (dry basis) of KOH pellets in one liter of diglyme (dimethyl ether of diethylene glycol) are heated with stirring at 170 C. The heterogeneous mass is cooled to 60 C. while continuously and vigorously agitated. The introduction of acetylene produces an exothermic reaction. The flask is externally cooled so that the temperature is kept at 60 C.:10 C. The addition of acetylene is terminated after 3 moles are absorbed. The temperature is then lowered to 25 C., and such a suspension can be used in alkylation with dihalides.
  • Example 39 Lithium amide, prepared in liquid ammonia from 21.0 g. (3.0 moles) of lithium, is reacted with 2.0 moles of dry acetylene to produce a 1:1 molar ratio mixture of monoand dilithium acetylide. Alkylation with 345 g. (1.5 moles) of pentame-thylene dibromide gives 61 g. (51% yield) of 1,8-nonadiyne and a higher boiling liquid which via vacuum distillation yields 1,8-cycltetradecadiyne and a filtrate. Heating the filtrate yields 20.8 g. clear liquid B.P. 11080 C. 0.1 mm. Hg (1,8,15-hexadecatriyne).
  • Example 40 Potassium amide, prepared from 117.3 g. (3 moles) of potassium in liquid ammonia, is reacted with 2.0 moles of acetylene to yield a 1:1 molar ratio mixture of monoand dipotassium acetylides. This mixture excess) is alkylated with 311 g. (1.35 moles) of 1,5-dibr0mopentane. There is thus obtained a mixture of 36.1 g. of 1,8- nonadiyne, 6.6 g. of 1,8,15-hexadecatn'yne and 7.8 g. of a yellow, amine-smelling liquid.
  • Example 41 Barium amide is prepared in liquid ammonia by adding 49.4 g. (0.36 mole) barium metal to the ammonia; dry acetylene (0.54 mole) is passed in to provide a 1:1 molar ratio of monoand dibarium acetylides. Alkylation is carried out by adding 69 g. (0.30 mole) of 1,5-dibromopentane. There is thus obtained 3.3 g. of 1,8-nonadiyne (n 1.4500), 3.3 g. of 1,8,15-hexadecatriyne (11 1.4772) and 0.5 g. of 1,8-cyclotetradecadiyne (M.P. 95 100 C.)
  • n is a number greater than 0; R and R are alkylene radicals having at least 5 carbon atoms. 2.
  • a cyclic polyyne having the structure:
  • R and R are alkylene radicals having at least 5 carbon atoms.

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3390197A (en) * 1966-05-13 1968-06-25 Procter & Gamble Novel tricyclic compounds and novel processes for producing tricyclic compounds
US20110136934A1 (en) * 2008-07-03 2011-06-09 Anthony N Jarvis Polychromic Substances and Their Use

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2846491A (en) * 1955-12-13 1958-08-05 Air Reduction Reactions of sodium acetylide with alkyl halides

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Publication number Priority date Publication date Assignee Title
US2846491A (en) * 1955-12-13 1958-08-05 Air Reduction Reactions of sodium acetylide with alkyl halides

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3390197A (en) * 1966-05-13 1968-06-25 Procter & Gamble Novel tricyclic compounds and novel processes for producing tricyclic compounds
US20110136934A1 (en) * 2008-07-03 2011-06-09 Anthony N Jarvis Polychromic Substances and Their Use
US8507178B2 (en) * 2008-07-03 2013-08-13 Datalase, Ltd Polychromic substances and their use

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