US3296321A - Cyclic acetylenic hydrocarbon preparation - Google Patents

Description

United States Patent 3,296,321 CYCLIC ACETYLENIC HYDROCARBON PREPARATION Bobby F. Adams, Painesville, and John H. Wotiz, Mentor,

Ohio, assignors to Diamond Alkali Company, Cleveland, Ohio, a corporation of Delaware No Drawing. Original applieationAug. 6, 1959, Ser. No.

831,930, now Patent No. 3,207,804, dated Sept. 21,

1965. Divided and this application Dec. 11, 1964, Ser.

15 Claims. (Cl. 260-666) This is a division of application Serial No. 831,930, filed August 6, 1959, now US. Patent No. 3,207,804, issued September 21, 1965, which in turn is a continuation-in-part of application Serial No. 769,583, filed October 27, 1958, now US. Patent 3,052,734, issued September 4, 1962.

This invention relates to novel polyynes comprising linear alpha, omega, polyacetylenic hydrocarbons and cyclic polyacetylenic hydrocarbons prepared by'chemically reacting an organic dihalide with a compound conh taining the linkage C=C, and to novel methods of preparing and using polyynes.

The present invention comprises the process illustrated by the following equation and certain novel products thereof:

Patented Jan. 3, 1967 "ice as well as corresponding ortho and meta radicals, oxygen, sulfur, mercury, boron, boron-containing radicals such as y o m a B halogen to 4-nlkyl heterocyclic radicals such as aryl substituted alkylene radicals, e. g.,

u cEo-E(GH2),(R molsn),o;.o3M X(oH2)e(R )i( Hz)= d (I) (II) I I (ormqHozo-aom). Lit -CEO'-E'(GH2)n )b (C 2)efCEO-}T( H2)e )F'"( 2)g 1 -,l-,(R)s y, l l d y Han-C501 (4311,

(III) (IV) wherein 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.. sodium, potassium, rubidium, lithium and cesium; alkaline earth metals, i.e., calcium, strontium and barium; and hydrogen; with the proviso that only one of M and M can be hydrogen; 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 from the group consisting of alkylcne, e.g., radicals having the structure -C H (and corresponding branched chain radicals), wherein m is a number from 1 to arylene,

alkyl 1 to 4 wherein M isselectedfromthe groupconsistingof calcium, barium, z inc, tin, lead,

| BP-CHzCHzCHPSF-C HzCHaGHzCHn-Br Cl (CH Cl Novel linear compounds of this inveniton are hydrogenended compounds having the following structure:

wherein M M, a, b, c, d, e, f, g, y, R and R are as defined hereinbefore. T

A preferred linear polyyne of this invention'has the structure:

wherein Z is an alkalene radical, h is a number from 3 to 10, inclusive, and i is a number from 2 to 10, inclusive.

The term 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. Specific examples of allHa Hr-CH:

112-011: More particularly, 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:

wherein 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 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:

(VI) HCECR7-CECR8CECH wherein R and R are alkylene radicals containing 2 to about 50 carbon atoms, inclusive. Specific illustrative triacetylenic hydrocarbons of this invention are:

1,9, l7-octadecatriyne 1,8,15-hexadecatriyne 1,7,13-tetradecatriyne 1,6,11-dodecatriyne Further illustrative linear compounds of this invention are alpha, omega tetraacetylenic hydrocarbons which may be represented by the structure:

wherein 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:

1,7,13,19-eicosatetrayne 1,8,15,22-tricosatetrayne 1,9, 17,25 -hexacosatetrayne 1,10,19,28-nonacosatetrayne Novel cyclic compounds of this invention have the following structure:

wherein 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.

Still more specifically, preferred novel cyclic acetylenic hydrocarbons Within the scope of this invention may be represented by the structure:

wherein 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:

1,7-cyclotridecadiyne 1,8-cyclotetradecadiyne 1,9-cyclopentadecadiyne 5 1,10-cyclohexadecadiyne 1,7, 13 -cycloctadecatriyne l,8,l-cycloheneicosatriyne 1,9,l7-cyclotetracosatriyne 6 METHOD A L E (XI) X(CH2)nX Na-CEC-Na (XII) Thus, such compounds can be prepared via the reaction: 5 1 C50 -II'C C- (CI 2)nCEC H (GHQ 3 ((111),. X CH 1X rr-ozo-rr L Jr l i) 1 1,0 (x is even or odd) l 0:0 (XIII) (XIV) l METHOD B HOEC-E(CH2) CEC-:} H ru)p (CH3) X orr, ,.X Na-GEC(CHr)nC C- i I EI land/or {fig} n L o 0% XIII x v when x=odd number (even number of triple bonds) wherein M is as previously defined and preferably an N g: g alkali metal, e.g., Na, X is chlorine, bromine or iodine, l qggmx a a 2 m is a number from 3 to 40, m is a number from 3 to 40, 2O NfiCECWHQmCECH n is a number from 1 to 10,000, p is a number from 5 I" I t to 40, and q is a number from 5 to when a large value =Q(CH:)NOCIHV+ of n is desired, no MCEC-H is employed. 0:0

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 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.

q 3HCEC-H+5NaNH NaC: -CNa+ NaCECI-I wherein M is a metal, cg Na r is a number f m 1 to An equivalent excess of I, XI and XII over the reactants 40 s is a number f 1 to 40 and n is an odd number II and X is desirable to minimize the amountof halogengreater than one; p and q being as already defined. 40 terminated p yy a m I As indicated previously hereinbefore, Compounds III (XV) HCEC{(CH -CEc} -(CH halOgI1 and V of this invention can he PFOdUCed y reacting a The thus-obtained alkali metal ended products are concompouhd Producing the linkage and a dihalo verted to hydrogen-terminated products during the typical alkylehe; more broadly Stated, such'compouhds can he work-up of the reaction,,e.g., addition (as by washing) produced by reacting Compounds I and II. a of water causes hydrolysis.

The expression p und P C g the linkage Referring to Methods A and B, 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- Although 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, strontium, beryllium and magnesium Hons sue as a acetylides. For convenience in describing the invention, 2)H H\- particular reference will be made hereinafter to alkali 2)n -l- E metal acetylides as illustrative of such reactants and as may be responsible for the presence of linear polyynes constituting a presently preferred type of reactant. in cases which do not contain any NaCEC Na.

The following two equations more specifically illus- Some representative products of this invention are set trate the reactions involved: forth in the following table:

Polyyne Type 11 x M.P.G. B.P. C. Mm. Method A A B A A 1 A VIII l 3 71 215 0.2 B z)A 2)r-O O(CHZ)4CEC(CHQ)-L 75 A cH (orn i 7 83 0.08 c

Furthermore, if one reacts X(CH ),,X with given ratio of mono to disodium acetylide (say 1:1), the yield of cyclic product increases with an increase in dilution. For example, 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. Higher dilution separates the molecules giving less chance for intermolecular interaction (linear product). If a molecule has a functional group capable of interaction, e.g., NaCEC(CH C.= C(CH X, then intramolecular reaction (formation of cyclic product) is favored by higher dilution. However, if the two reactive ends cannot get together (because of size or shape of the molecule), no cyclic product will be formed no matter what dilution is employed. Thus, the amount of 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. Conversely, 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.

2Na+HC ECH NaCECNa 2NaNH +HCECH NaCECNa NaCECH+NaNH NaCECNa A discussion of the preparation of disodium acetylide, sodium amide, and of the above reactions may be found in Inorganic Synthesis, vol. 2, Editor-in-Chief W. Conrad Fernelius, the McGraW-Hill Book Company, Inc., New York 1946), pages 75 and following.

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.,

3NaNH-g 2HCECH NaCECH NaCECNa 4NaNHz BHCECH 2NaO CH NaCEONa 5N1NH2 3HCECH NaCEOH QNaOECNa Since NaNH is prepared in quantitative yield by the reaction of sodium with ammonia, the weight of used sodium determines the amount of NaNH present. Acetylene is measured with wet test gas meter, 1 mole(STP)= 22.4 liters.

As stated, 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. These reactants are combined in essentially stoichiometric ratios; however, considerable departure from these ratios may be tolerated, such as up to about %15% departure from these ratios, without serious detriment to either quality of product or yield; an equivalant excess of the disodium acetylide being preferred when a hydrogen-ended product is desired.

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. Such 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,

propanol, butanol and isopropanol and acids such as Ca+ 2N3. QNH; 2N3NII: H3 zNaNr-r, HCECH NaGECNa 2NH'.

NaOEONa XRX Compound III and IV wherein XRX is compound II, defined previously. Al though liquid ammonia is the preferred solvent for these reactants, other organic solvents, such as amines, e.g.,

butylamine, ethylenediamine, triethylamine and diethyl:

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. Normally, 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,

Specific illustrative preparations involving the reaction of disodium acetylide and an alkylene dihalide are the preparation of compounds of structures VI and VII above. Although 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.

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.

Illustrative of the foregoing and other specific compounds of this invention arethe following compounds having the indicated structures:

cEccH cEc H 1,8,15,22-tricosatetrayne 1,7,13,19,25-hexacosapentayne LC EC 1,8-cyclotetradecadiyne i-C EC-1| 61195 (CH2):

-OEG- 1,8-cyclopentadecadiyne ||CEO (CH2) a (01305 10 1,9-cyclohexadecadiyne CEC Compounds within the scope of structures VIII and IX may be prepared by chemically reacting a dialkali metal acetyli-de and an alkylene dihalide under essentially the same reaction conditions employed for the preparation of a. linear alpha, omega polyacetylenic hydrocarbon; that is, the cyclic hydrocarbon may be and is normally prepared as a by-product in the preparation of the linear hydrocarbons. The formation of 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.

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.,

CEO (CH2)5 (CHM HCEC (CH2)5OEO(CHQ)5GECH CEO Solid Liquid linear Hg derivatives no reaction The linear polyynes may be regenerated on acidification with dilute HCl.

this invention exhibit activity as insecticides, fungicides,

herbicides and nematocides.

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.

Thus, it 'will be appreciated that compounds of this invention may be employed to form biologically active substances containing such compounds as essential active ingredients which 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.

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). 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).

The term 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.

Moreover, 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.

Still further, the compounds of this invention are useful in the inhibition of decomposition of a halogenated aromatic hydrocanbon. In this application it has been found that decomposition of a halogenated hydrocarbon, e.g., a chlorinated xylene, may be prevented by the addition thereto of a stabilizing amount of a compound according to the structure:

wherein 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.

It is known that 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. However, in many instances obtaining such high purity chlorinated xylene in commercial production is not feasible. 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. Hence, means for preventing and/or inhibiting this decomposition of chlorinated xylenes and/or other chlorinated aromatic hydrocarbons generally associated therewith are highly desirable.

Previously various stabilizers for aliphatic chlorinated hydrocarbons have been employed. Some of those compounds which have demonstrated a degree of effectiveness are acetylenic alcohols, acetylenic ethers, straight chain acetylenic esters, monoacetylenic hydrocarbons and monoacetylenic monoolefiuic hydrocarbons. these prior stabilizers enjoyed a certain amount of success, surprisingly, such materials are not satisfactory for the stabilization of chlorinated xylenes and specifically alpha-chloro-p-xylenes for various reasons. Acetylenic alcohols are highly effective for the stabilization of such chlorinated. 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.

In view of the fact that the above acetylenically unsaturated general stabilzers employed are unsatisfactory,

it would lead to the conclusion that the 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. For the most part the purity of such 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.

Where the initial purity is not tolerable 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. As noted above, 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.

It has been found that the chlorinated,

Although i In general, 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.

Further, the present invention is directed to a composition comprising essentially benzyl chloride and a stabilizing amount of at least one cyclic acetylenic hydrocarbon, e.g., 1,8-cyclotetradecadiyne.

Further, 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. Typical stabilizer combinations of 1,8,15-

hexadecatriyne and bis-(Z-propynl)-2,3,5,6-tetrachloroterephthalate, 1,8,15-hexadecatriyne and sorbitol, and 1,8- cyclotetradecadiyne and ethylene glycol. It will be understood that the invention is not limited to a particular light, heat, or other stabilizers, and that, in general, any well-known light or other stabilizer may be employed with the general purpose stabilizers of this invention.

As stated, 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. For the most part, 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, i.e., chlorinated aromatic hydrocarbons, in accordance with this invention 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. It is preferred that 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.

Other applications of 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.

Other applications and uses will be apparent to those skilled in the art in view of the following specific examples. These examples are offered in order that those skilled in the art may more completely understand the present invention and the preferred methods by which the same may be carried into effect.

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. (2.2 mol) of pentarnethylene dibromide is added at a fast dropwise rate sufiicient to retain gentle refluxing ammonia. Upon completion of addition of the dibromide, agitation of the mixture is increased to wash down the splattered material on the sides of the reaction flask. The reaction is then stopped and the openings of the reaction vessel covered with polyvinyl chloride film, the reaction mixture being allowed to stand overnight. The reaction mixture is then agitated while water is added slowly with caution. The pressure is vented by loosening the plastic sheets covering the reaction vessel opening. Upon addition of about 400 ml. of water, the reaction vessel walls are washed by increasing the agitation. 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:

Element Actual Percent By Weight Calculated Percent By Weight Infrared spectra indicate the presence of internal acetylenic linkage and the absence of terminal acetylenic linkage; in addition, the compound is insoluble in water and soluble in acetone, cyclohexanone and xylene.

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:

Element Actua] Percent By Weight Calculated Percent By Weight Infrared spectra also indicates the desired product.

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.

The combined ether extracts are washed with dilute -hy-- drogen chloride and dilute sodium carbonate aqueous solutions and dried over calcium sulfate. Ether is then removed through distillation. The resultant product is distilled with 1,7,l3-tetradecatriyne, C H boiling at 111 to 112 C. at 1.0 mm. mercury pressure and an additional product, 1,7,13,19-eicosat6trayhe, cgoHge, boiling at 165 to 170 C. at 0.3 mm. mercury pressure. The above triyne is indicated by the following analytical data:

Element Actual Percent By Calculated Percent Weight By Weight 89.2 90. 2 H 9. 6 0. 8 Molecular Weight 188 186 The above tetrayne .is also indicated by the following elemental analytical data:

Element Actual Percent By Calculated Percent Weight By Weight C S9. 3 90. 2 H 9. 8 9. 8 Molecular Weight 276 266 Other higher polyynes are also formed as by-products of the above reaction. The desired products are also indicated by infrared spectra.

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-

acetone0.0l% Triton Xl55- balance Water) until they are thoroughly wetted. The chemical deposit on the leaf is then dried and the paired leaves are separated. Each is placed in a 9 cm. Petri dish with a filter paper liner, and ten randomly selected larvae are introduced before the dish is closed. After three days exposure, 100% mortality is observed.

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:

TABLE I Percent roach mor- 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 ,8

In order to evaluate systemic fungicidal activity, tomato plants, variety Bonny Best, growing in 4-inch pots are.

treated by pouring a test formulation (2000 p.p.m. product of Example 15% acet0ne0.0l% Triton Xl55' balance water) on the soil in the pots at a rate equivalent to 128 lbs/acre (102 ing/pot). The tomato plants are 3 to 4 inches tall and the trifoliant leaves are just starting to unfold at time of treatment. The tomato plants are exposed to the early blight fungus so that at the time of treatment, infection has occurred. After 10 to 14 days observation indicates greater than 45% disease control.

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. In this procedure, 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. These 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,

the following compounds were rated according to their activity in this test:

1 7 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:

xample 3) 1,8,l5-l'11exadecatriyne (Product of Exa 18 about 4 inch of soil and watered. After 24 hours, 80 ml. of an aqueous test formulation (320 mg. test chemical 5% acetone-0.0l% Triton Xl55--balance water) uniformly over the surface of the pan. This is equivalent to 64 lbs/acre. The seed mixture contains representatives of three broadleafs: turnip, flax, and alfalfa, and three grasses: wheat, millet, and rye grass. Two weeks after treatment records are taken on seedling stand as compared to the controls. Using this procedure the following results are indicated:

TABLE V Broadleaf Grass Plants Plants 1,7,13,19-eic0satetrayne (Product of amp 2) 1,7,13-tetradecatriyne Example 14 To test herbicidal activity of the product of Example 1, tomato plants, variety Bonny Best, 5 to 7 inches tall; corn, variety Cornell Ml (field corn), 4 to 6 inches tall; bean, variety Tendergreen, just as the trifoliate leaves are beginning to unfold; and oats, variety Clinton, 3 to 5 inches tall, are sprayed with an aqueous test formulation (6400 p.p.m. test chemical5% acetone0.0l% Triton X-lbalance water). The plants are sprayed with 100ml. at 40 lbs. air pressure While being rotated on a turntable in a spray hood. Records are taken 14 days after treatment and phytotoxicity is rated on TABLE III Compound Tested E. Amylovom X. phaseoli S. aureus E. coli 1, 7, 13-tetradecatriyne- 90 70 40 10 1, 7, 13, l eicosatetrayne 40 0 40 0 Example 12 a scale from 0 for no injury to 11 for plant kill; Using Seeds of green foxtail and lambs quarters are treated in Petri dishes with aqueous suspensions of the test chemical at 1000 and 100 p.p.m. (1000 or 100 p.p.m. product of Example 35% acetone-0.01% Triton X-l55balance water). Lots of 25 seeds of each type. are scattered in separate dishes containing filter paper discs moistened with 5 ml. of the test formulation at each concentration. After 7 to 10 days under controlled conditions, the test compound is given a rating which corresponds to the concentration that inhibits germination of half of the spores (ED 50) in the test or greater. Using this test, the following results are observed:

TABLE IV Concentration inhibiting germination of half of the seeds Compound Tested Lamb's Quar- Green Foxtail,

ters, p.p.m. p.p.m.

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),

this procedure the product of 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 Example 16 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. In this test 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. A series of six solutions is made up in this manner, the last solution being employedas a standardized check. Each of these solutions is allowed to stand at room temperature for 9 days in the presence of ordinary room light whereupon each of the solutions is rated on a scale from for colorless to 10 denoting complete decomposition and high discoloring. Employing this procedure, the standard check solutions were completely black receiving .a rating of 10 at the end of the period employed, whereas the stabilized solutions were colorless, receiving a rating of 0. Thus demonstrating that 1,8,15- hexadecatriyne is singularly elfective in the stabilization of alpha-chloro-p-xylene for a period of greater than 9' days under the conditions employed.

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. In this test 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 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. of the triyne and 0.125 g. of ethylene glycol is added to the third, respectively. A metal contaminant comprising 50% iron powder and 50% iron oxide is then added on concentrations from about 0.01 g. to 0.5 g. per container. A series of four solutions is made up in this manner, the latter solution being employed as the standardized check. Each solution is allowed to stand at room temperature for 16 days in the presence of ordinary room light, whereupon each of these solutions is rated on a scale from 0 for colorless to 10 denoting complete decomposition and high discoloring. Employing this procedure the standard check solutions were completely black at the end of the period employed whereas the stabilized solutions were colorless, receiving a rating of 0. Thus demonstratingthat the combination of 1,8,l-hexadecatriyne and ethylene glycol is synergistically effective, stabilizing alpha-chloro-p-xylene for a period of better than 15 days under the conditions employed.

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.

of 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.

catalyst prepared by the method set forth in Organic Reactions, vol. 5, pp. 48-49. Dry acetylene is then metered into the suspension of sodium amide in ammonia until the desirable ratio of mono to disodium acetylide is reached, i.e., 1:1 or 2:1. The dihalide is added dropwise and the reaction mixture stirred under reflux for four hours. The Dry Ice-acetone condenser is removed, the opening covered with a cellophane film, and the ammonia is permitted to evaporate over a 16-hour period. Thev residue is diluted with water and, if the organic portion is not sulficiently liquid, it is dissolved in ether. The organic layer is washed, in succession, with dilute hYdlO'.

chloric acid, sodium carbonate, water and dried over.

magnesium sulfate. The products are separated by fractional distillation. In reactions where n is 5, the disti1la-.

tion is temporarily interrupted after the diyne and triyne (II, x=1 and 2) are collected. On cooling, the cyclic.

diyne III (x=1) crystallizes and is removed by filtration.

Fractional distillations at 0.1 mm. are continued until a pot temperaure of 350 is reached. The pot residue is I frequently only tan-colored and of vasoline-like consistency. Fractions of narrow boiling range are redistilled 1 or crystallized from appropriate mixtures of ether-.

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.

TABLE I o NaCEC-.Na X a BHCHmBr H-c =.c-[ om).c=c- .-H (v (on. (0111).. (37111 Mo]. w ht Polyyne Type n x Calcd. Found Calcd. Found elg Calcd. Found v 4 2 90. a 89.2 9. 7 9. 0 186 188 v 4 a 90. 2 s9. 3 9. s 9. s 266 276 v 4 7 90.1 88.5 9. 9 10.2 586 597 v 4 s 90. 1 86. 9 9. 9 10.2 666 666 v= 5 2 89. 5 88. a 10. 3 10. 3 214 203 s 2 2 as as 1 9 308 0. 10. 242 237 H-OEO(CHZ)O(CH;)4CECHI 81.0 79.4 101 9.9 178 164 VIII 5 1 89.3 89.6 10.7 10.6 198 182 VIII9- 4 3 90. 0 s9. 5 10. 0 9.8 320 270 prime E0 (CH h-O 79. 0 79. 1 10.5 10.6 304 279 V See footnote at end of table.

TABLE IContinued Characteristic LR. Bands 13.1.

p (intensity) M.P., Polyyne Type C.

C E 0. mm. HO CH Hg (Rocking) Terminal Internal V 111 1.0 3.02vs.-. 4.70m 4.47VW 13.62w. V 167 0. 3 3.02vs--. 4.70m 4.47vw 13.55W. V 36 3.05W 13.55VW. V 55 3.05W 13.55vw. Va--- 113 0.8 3.07vs 13.80111. V- 170 0.1 33 3.02s V- 131 0. 2 24 3.04vs 13.82111. HC C(CH2)40 '(CH2)4C C H 130 30 3.05vs VIIL 100 13.645. me 215 0. 2 71 13.60w. (CH2)4C C(CH) O 175 0.1 75

O-(CHz)4C C (CH2);

Norm: An equivalent excess of about 25% to 50% Na over Br is used.

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:

(a) HCEC(CH2)40(CH2)4CECH, 19.5 g., colorless liquid, B.P. 130 at 30 mm., n 1.4577.

Analysis.Calcd. for C H O: C, 81.0; H, 10.1; M.Wt. 178. Found: C, 79.4; H, 9.9; M.Wt. 165. The infrared spectrum contains the characteristic absorption bands of CECH near 3.05 and 4.74,:1.

5 g., R1. 180 at 0.08 mm., M.P. 74-5 (colorless crystals).

Analysis.Calcd. for C H O C, 79.0; H, 10.5.

Found: C, 79.1; H, 10.6. The infrared spectrum shows it to be free of absorption bands characteristic of a terminal triple bond. The-internal triple bond was evident from the absorption band near 4.5 0 1.

The 5-hexynyl ether exhibits activity as a contact poison against roaches, as a systemic rust fungicide and as a bactericide.

Example 22.Preparati0n of Sodium amide is prepared from 47 g. (2.05 mol') of sodium in 3 liters of liquid ammonia at 32. A 1:1 mixture of NHCECH and Na-C-=-CNa is prepared by metering into the suspension 1.37 moles of acetylene. Alkylation is effected by the addition of 200 g. (0.82 mol) of Br(CH) Br. Stirring is maintained for 48 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. Repeated distillation yields 27 g. of colorless liquid, B.P. 1309 at 0.2 mm., 11 1.4772 to 1.4806,

I spectrum contains bands near 3.04 and 4.72 characteristic of terminal triple bonds. 7

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. of the starting nonadiyne, and 26 g. of 1,8-cyclotetradecadiyne. Further distillation yields a fraction boiling from 170 at 0.1 -mm., which solidifies on cooling to room temperature. Crystallization of this fraction from ether gives 25 g. of the solid l,8,1S,22-tricosatetrayne, M.P. 32-3".

Analysis.-Calcd. for C H C, 89.6; H, 10.4; M.Wt. 308. Found: C, 89.1; H, 10.6; M.Wt. 279. Its infrared spectrum contains bands near 3.02 and 4.72 1, characteristic of the terminal triple bond.

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.

Analysis.-Calcd. for C H C, 89.9; H, 10.1; M. Wt. 160. Found: C, 89.5; H, 10.2; M.Wt. 152. Its infrared spectrum is free from absorption bands, characteristic of a terminal triple bond. Further distillation produces a yellow oil, B.P. 210-220 at 0.2 mm. Hg which partly solidifies on standing. Crystallization from a mixture of ether and pentane yields 1,7,13,19-cyc1otetracosatetrayne as a white solid, M.P. 7 71 Analysis.Calcd. for C l-I C, 90.0; H, 10.0. Found: C, 89.5; H, 9.8. Its infrared spectrum is free from absorption bands characteristic of a terminal triple bond.

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.

Analysis.Calcd. for C H C, 89.7; H, 10.3; M.Wt. 174. Found: C, 89.0; H, 10.3; M.Wt. 171. The infrared spectrum is free of bands characteristic of a terminal triple bond.

Further to illustrate the preparation of other compounds of the invention, the following examples are provided wherein the quantities and steps designated (a) and (b) refer to the preparation of a mixture of mono and disodium acetylide, and step (c) refers to the alkylation, all accomplished via the procedure of the foregoing five examples. 7 Example 26.Preparafi0n 0f HCEC(CH )3CEC(CH CEcH (a) NH 3 liters; NaNH 2 M from 46 g. (2 M) of Na (b) HCECH, 1.5 moles yielding a 2:1 ratio of NaC CH to NaC-=CNa (c) Br.(CH Br, 161 g. (0.8 mole) 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. (0.8 mole) (a) NH3, f liters;'NaNH 2 moles from 46 g. 2 M) (b) H-CEC(CH2)5CEC-H, 60 g. (0.5 mole) (c) Br(CH Br, 122 g. (0.5 mole) mole) (c) Br(CH Br, 108 g. (0.5 mole) Example 33.Preparati0n of (CHz)5'"CE 2)5 EC(CH2)5OE (a) NH 4 liters; NaNH 1 mole from 23 g. (1 M) of (b) H-CEC(CH2)5CEC(CH2)5CECH, 107 g. (0.5.

mole) (c) Br(CH Br, 115 g. (0.5 mole) Example 34.Preparati0n 0f (GH2)6OEC(CH2)6 EC-(CHz)a'CE -(a) NH 4 1iters; NaNH 1 mole from 23 g. (l M) of Na (b) HCEC(CH CEC(CH CECH,

mole) (c) Br(CH Br, 122 g. (0.5 mole) Additionally to illustrate the preparation of mixtures of mono and disodium acetylide, the following examples are 1' provided:

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.

A Example 36 A 5-1iter three-necked flask is fitted with a reflux con denser, stirrer and gas inlet tube. Ninety-two g. (4 gram atoms) of a sodium dispersion (IO-25 microns particle size, containing 0.25% of aluminum stearate and 0.5% of 1 oleic acid) in 4 liters of xylene is heated to 105 C. Purified acetylene (passed through 90% H and a column. filled with activated alumina) is introduced under the sur-: 1 face of the suspension. A total of 78.4 liters (STP, 3.5

To analyze the reaction product a small sample of the produced solids is treated with water and the liberated gas analyzed by means of vapor chromatography. Qnly acetylene is produced, indicating the absence of unreacted sodium in the solids.

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.)

It is to be understood that although the invention has been described with specific reference to particular embodiments thereof, it is not to be so limited, since changes and alterations therein may be made which are within the full intended scope of this invention as defined by the appended claims.

What is claimed is:

1. A cyclic polyyne having the structure:

Re -CEO EGEWRAQ wherein 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:

CEO

CEO

wherein R and R are alkylene radicals having at least 5 carbon atoms.

3. The method of preparing a cyclic, acetylenic hydrocarbon which comprises chemically reacting a dialkali metal acetylide with an alkylene dihalide.

4. The method of preparing compounds of the struc- References Cited by the Examiner UNITED STATES PATENTS 8/1958 Rutledge 260-678 OTHER REFERENCES Donald J. Cram et al.: J. Amer. Chem. Soc., 78, pp. 2518-2523, June 5, 1956.

John H. Wotiz et al.: J. Amer. Chem. Soc., 83, pp. 373376, June 20, 1961.

DELBERT E. GANTZ, Primary Examiner.

V. OKEEFE, Assistant Examiner.

Claims (1)

1. A CYCLIC POLYYNE HAVING THE STRUCTURE: R3<(-C*C-(R4-C*C)-) WHERIN N IS A NUMBER GREATER THAN 0; R3 AND R4 ARE ALKYLENE RADICALS HAVING AT LEAST 5 CARBON ATOMS.