US2933529A - Symmetrical diquaternary ammonium compounds - Google Patents

Description

mula

' Z-nonenyl,

SYMMETRICAI. DIQUATERNARY AMMONIUM COMPOUNDS Jesse C. H. Hwa, Levittown, Pa., assignor to Rohm 8: Haas Company, Philadelphia, Pa., a corporation of Delaware N Drawing. Application January 9, 196 Serial No. 557,836

15 Claims. ((11.260-567.6)

The present invention relates to novel symmetrical diquaternary ammonium compounds and to a method for their preparation.

The symmetrical diquaternary ammonium compounds of the present invention may be represented. by the for- X Rl 34 X 7 p in which R, is preferably an alkyl group of no more than two carbon atoms, R is preferably an alkenyl group of eight to twenty carbon atoms, E is preferably an alkylene group of twoto four carbon atoms, and X is preferably a halogen having an atomic weight of about 35.5 to 127.

The symbol R preferably represents a methyl or ethyl group, that is, an alkyl group of no more than two carbon atoms. The two R groups on each of the nitrogen atoms may be taken collectively to represent a divalent saturated aliphatic chain of four to five atoms which jointly with the amino nitrogen atom forms a fiveto six-sided monoheterocyclic amine group such as morpholino, thiamorpholino, pyrrolidinyl, and piperidino groups, and these groups having a lower alkyl substituent, such as a methyl or ethyl group.

The symbol R is preferably an alkenyl group of eight to twenty carbon atoms. Actually, R may be any aliphatic group, of the stated size, that has at least one bond of unsaturation. That is, there may be used alkenyl, alkdienyl, alkynyl groups, and the like, of eight to twenty carbon atoms. The R group may be a straight or branched chain, preferably branched in any'of the known spatial configurations and the bond or bonds of unsaturation may be at any possible locations. For'instance, when R is dodecenyl possible groups include ndodecenyl, isododecenyl, 1,10-dir'nthyl-2-decenyl, 2,7-dimethyl-2-decenyl, 1-ethyl-2-methyl-5-nonenyl, 4-propyl- 5-butyl-2-octeny1, 1,2ediethyl-4-octenyl, 1- propyl-6-ethyl B-heptenyl, and the like. A common commercial form' of the dodecenyl group that yields a compound of this invention that is particularly effective for the present purposes is tet'ramethyloctenyl, in which there are two methyl groups on each ofLthe number five and seven carbon atoms and the double bond'is at the number two location. Typical of the R representations include octenyl, nonenyl, decenyl, dodecenyl, tetradecenyl, pentadecenyl hexadecenyl, octadecenyl, nonodecenyl, eicosenyl, octadienyl, decedienyl, dodecadienyl, octadecadienyl, octynyl, dodecynyl, and octadecynyl.

The symbol X is preferably a halogen having anatomic weight of about 35.5 to 127, i.e., chlorine, bromine, or

iodine. Chlorine is the preferred representation of X. It will be apparent to one skilled in the art that other anions may be satisfactorily employed such as sulfate, methylsulfate, phosphate, acetate, citrate, tartrate, and the like, which may be supplied directly or by metathesis with the halide form of the present compounds or by Patented Apr. 19, 1960 the use of an anion-exchange resin. Generally, an anion be present a single hydroxyl substituent; E may be em- 'ployed in any of its isomeric forms. v

It is essential for the present purposes that the groups R R and X be the same on each of the nitrogen atoms, that is, the present compounds must be spatially symmetrical about the nitrogen atoms with respect to R R and X. The compounds of this invention, in order to be effective for the present purposes, are restrictedas to the size and identity of the substituent groups, the symmetrical molecular configuration, and the presence of aliphatic unsaturation, and preferable branched skeletal structure, in the R groups.

The quaternary ammonium compounds are preferably prepared by bringing together at a reacting temperature, and thereby causing to react, a compound having the formula R1 l R] .N EN R1/ Rr with a compound having the formula R X. The results are generally essentially quantitative. The reaction involves the union of the R X and compounds on a two to one molecular basis in order to form the symmetrical diquaternization products of this invention. If desired, the R X reactant may be used in excess in order to assure completeness of reaction. Completeness of reaction may be indicated by the amount 'of ionizable anion formed, such as halide, and the disappearance of basicity. If an excess of R X is employed it may be removed at the completion of the reaction by distillation or solvent extraction, as desired,

Reaction temperatures may be used in the range of about 25 'C. to the reflux temperature of the reaction mixture, preferably from 50 to C. orup to the reflux temperature, temperatures up to about 265? C. being practical. If desired, there may be used a catalyst,

such as a' polar iodide soluble in the reaction mixture.

Sodium iodide is preferred in this respect.

Reaction times of about two to twenty hours or more are generally employed depending largely on thereac'tion temperature, solvent, and individual reactants used. The

time of reaction is not critical butmerely influences the yield. -As willbe apparent to one skilled in the art, the longer reaction times generally favor higher yields, up to a point, and, of course, some reactants unite more speedily than others.

It is advantageous to employ a volatile inert solvent such as hexane, heptanei, benzene, toluene, ethyl ether, methanol, isopropanoL-Water, chloroform, acetone, 2-

butanone, acetonitrile, acrylonitrile, nitromethane, form- .ethane,

v 3 are substantially water soluble. The product may be washed, if desired, such as with hexane, heptane, and the like to remove unused starting materials. It is often not necessary to isolate the product, from the solvent, particularly if the solvent used is alcohol or water, since the product may be satisfactorily used for the present purposes in an aqueous or alcoholic solution.

There has been set forth, heretofore, the representations of E, X, R and R The reactants R X and R1 B! may be determined by combining the representations of the component parts previously listed. Typical of the reactants that may be employed as R X include octenyl chloride, nonenyl chloride, decenyl chloride, dodecenyl chloride, tetradecenyl chloride, hexadecenyl chloride, octadecenyl chloride, eicosenyl chloride, octad-ienyl chloride, decadienyl chloride, dodecadienyl chloride, octadecadienyl chloride, octatrienyl chloride, octynyl chloride, dodecynyl chloride, and octadecynyl chloride. The other anion representations of X, previously set forth, may be used in place of the illustrative chloride form presented above. The halide representation of X is preferred. Where more than one molecular location of X is possible in the reactant R X, all possibilities are contemplated as long as X is reactive in the present sense, that is, labile enough to undergo the present quaternization under the instant reaction conditions.

Typical of the reactants, having the formula that may be used include N,N-tetramethylethylenediamine, N,N'-tetraethylethylenediamine, N,N'-tetramethylpropylenediamine, N,N' tetraethylisopropylenediamine, N,N'-tetramethylbutylenediamine, 1,4-bis diethylamino 2-butene, 1,4-bis(dimethylamino)-1,3-butadiene, 1,4-bis (dimethylamino)-2-butyne, 1,2-dipiperidinoethane, 1,2- dimorpholinoethane, 1,2 dithiamorpholino 1 methyl- 1,4-dipyrrolidinylbutane, 1,4-dipiperidino-2-butene, l,4-dimorpholino-2-butyne, N,N'-tetramethyl-2-hydroxypropylenediamine, N, N'-tetraethyl-Z-hydroxypropylenediamine.

It is possible, and frequently advantageous, in the preparation of some of the present compounds to first prepare the halide form, such as chloride, in a manner already set forth, and then prepare any other desired form, within the present definition, by metathesis or ion-exchange methods. For instance, any of the present compounds in halide form, may be converted to the hydroxide form through the use of silver oxide, or the like, and then converted to any desired anion form by acidifying with an acid of choice such as sulfuric, phosphoric, acetic, and others within the range and spirit of this invention. In

CH3 CH3 CH: CH:

similar manner, an anion-exchange resin may be employed. Any of the present compounds, in halide or hydroxide form, maybe converted to any desired anion form through the use of an anion-exchange resin in the desired anion form. For instance, there may be used an insoluble, cross-linked, styrene-divinylbenzene copolymeric quaternary ammonium salt in its sulfate, phosphate, or like form to convert a present compound, in halide or hydroxide form, to a desired form, such as phosphate, sulfate, and the like.

vacuum desiccator.

The symmetrical diquaternary ammonium compounds of this invention are valuable non-durable anti-static agents for hydrophobic fibers, such as nylon, Dacron, and Orlon. They are useful fungicides, in a wide range of concentrations, for example, against Stemphylium sarcinaeforme and Monilinia fructicola. They are, also, effective bacteristats and bactericides in dilutions of up to 1:50,000 and greater, particularly against Micrococcus pyogenes var. aureus and Salmonella typhosa. The present compounds exhibit advantageous characteristics as wetting, emulsifying, and dispersing agents and as detergents.

The compounds of this invention are valuable as detergent-sanitizers and may be employed in meat plants to sanitize cutting tables, grinders, and the like, in fruit processing operations, for instance, to wash and sanitize lemons, oranges, and grapefruit, and in dairy farms to sanitize dairy equipment and utensils.

A suitable detergent-sanitizer formulation for use in meat plants includes, by weight, 5% of a compound of this invention, 2.5 to 5.0% of octylphenoxypolyethoxy- 'ethanol, 20 to 40% soda ash, 20 to 40% sodium metasilicate, and the remainder sodium tripolyphosphate. One ounce of this formulation is used per gallon of water. For sanitizing citrus fruit there is preferably used one part of a present compound in 5000 parts of water. For use in dairy farms, there may be used 10% of a quaternary ammonium compound of this invention, 10% of octylphenoxypolyethoxyethanol, 7% of trisodium phosphate, and 73% of water. One ounce of this solution is used per four gallons of water. The instant compounds in aqueous solution, in amounts of about 0.5 to one ounce to one hundred pounds of dry fabric, are excellent as a final diaper rinse to prevent diaper rash. These compounds are, also excellent premise sanitizers where they may be employed in concentrations of about 0.1 to 2.0% in aqueous cleaning solutions.

The symmetrical diquaternary ammonium compounds of this invention and their method of preparation may be more clearly understood from the following examples, which are presented by way of illustration and not by way of limitation. Parts by weight are used throughout.

Example I There are added to a flask equipped with a thermometer, a reflux condenser and a stirrer 98.5 parts of N,N'- tetramethylethylenediamine, 400 parts of dodecenyl chloride, one part of sodium iodide and 1000 parts of iso propanol. The mixture is heated at reflux for 20 hours. The mixture is then concentrated to about one third of its original volume by means of distillation. The resultant solution is chilled and the crystals that form are filtered, washed twice with acetone and then dried in a The white, hygroscopic, crystalline product contained 5.3% nitrogen (5.3% theoretical) and 13.6% chlorine (13.7% theoretical). The product corresponds to ethylenebis(dodecenyldimethylammonium chloride) and may be represented by the formula In like manner, there is made from N,N'-tetraethylbutenylenediamine and dodecenyl chloride the compound corresponding to the formula CnHra C2115 CaHs CnHza NCHzCH=CHCH2-N C CnHs 02H; 01

Example 2 There are added to a reaction flask 77.5 parts of an aqueous 75% N,N'-tetramethylethylenediarnine solution,

'mother liquor. .The 1combined aqueous solution contains 35 droxide ions.

I v V 251 parts of dodecenyl chloride (84.5% pure) and 225 and from N,N tetramethyibutylenediamine and 224,4 parts of water. The mixture is agitated and maintained tetramethyl-l6-chloro 6-hexadecene, thereis obtained the at 60-75 C. for 6 hours. The solution changes from compound having the formula CH: CH: V (311: C-H: c'n'r-c-onh -onzcn=oncmtcnin om crponmcrncihcncmc-crnh-om CH3" CH: IITT-C4HQ,III\ H; CH:

7 C(Cfia CH: 01

a yellow cloudy slurry to a clear-amber solution as the -Example 4 reaction progresses. After this heating, period, the equip- Y V inentis modified to remove distillate, and 200. parts of A mi of Parts Of '-tetr me y a water are added to themixture. Approximately 200 15 Ylenediamine, Parts of dodecenyl Chklfide a 300 parts of water plus some organic liq id removed by J parts of dry acetone is stirred at room temperature for this atmospheric distillation. The j'rnaining li id, 3 45 minutes. The solution is still clear indicating no clear dark amber solfltibn gorrespond t an aqueous substantial reaction has taken place at this temperature solution of the vproduct whieh contai 2.7% nitrogen and time. The solution is then heated to reflux and (2.7% theoretical) and 7:s%.eh1orine (6.8% theoretical) White precipitate startsto appearafter minutes. The for a 50% solution. Theyield is 100%. The product refiux continued fdi24 he' Aftereovling. t c y may he-nanied 'ethylen'ebis(dodeceiiyldimethylammonium tals that are formed are remeved y filtration; wa hed chloride). To 56 parts of the above aqueous solution Once With y acetone and dried n Vacuum The P of product, thereare added 224 parts of water-and 0,05 uct melts at 194-196 C. and contains 13.1% chlorine equivalent of freshly prepared moist silver oxide. The (12.9% theoretical) and 5.0% nitrogen (5.1% theoreti mixture is stirred well at room temperature forone hour cal). The product corresponds to this formula on, om 3H3 CH3 CHs-C-CHzlJ-CHgCH -CHCH: 0H; CH: Cfi2CH=CHCH2C-CH5CCH3 @113. '1 NCH2CHzCH2CH2N.. CHa. 10H:

and then filtered; The' r'esidue is washed twice with 40 parts of water, and the washings are combined with the In a sumlar a mh'ure of 14 Parts 14 his! methylarnino)-2-butyne, 49.7 parts of dodecenyl chloride and 350 partsof acetone 'givesoineprecipitate at room temperaturein 25 rninutes; After one hour of reflux, 300 parts of acetone is added to keep the mixture fluid. a The mixture is refluxed fora total ch14 hours. After Example 3 filtration, washing, and drying, the product is obtained. A mixture of 13 parts of N,N'-tetramethyltrimethylene- It melts at 207 209 C. and contains 13.2% chlorine diamine, 47.5 parts of dodecenyl chloride, 0.3 part of (13.1% theoretical) and 5.0% nitrogen (5.2% theoretisodium iodide, parts of isopropanol and 50 parts of cal). The products corresponds to this formula less than 0.1% chlorine and indicates that about of .the original .chloride. ions... havebeen replaced by hy- CH9 1 CH3 IIT-CHzCECCHzN CH3 CH3 0 CH3 OHsCl acetone is refluxed for 16 hours during which time 43 In a similar way, from ethylenedi-N,N'-piperidine and parts of solvent is removed by distillation. The mixl-bromo-2,4,6-octatriene, there is made the compound of ture is cooled. The crystals that separated out are this invention corresponding to the formula ofi,cH=0HOH=oHoH =oHcHi cHioHt CHzCH =CHCH=CHQH=CHYGHz Br-N N-Br (TH; E: @112 cm cm CH2 cm CH2 CH2 7 washed twice with hot acetone and twice withvcold ace Example '5" tone and dried under vacuum over calcium chloride. r The white crystalline product melts at 10159-103" C. A mixture of 172 Pa N.N'-tetraethylethylenedi- (with decomposition) and. contains 13.6%. chlorine 5 amine, 44.6 parts of l chloro 5-methyl-2-undecene, 0.5

( tfiiol'etigal) and i i2 part of sodium iodide and partsof dry acetone is recal) 6 Pro uct coirespqn mme ye'ne fluxed for 16 hours. Thesolution is concentrated by methyldodecenylammonium chloride).

In a similar way, from N,N'-tetraethylethylenediamine dlstluatlon and 300 Parts of Wa The mlxmre nd h xade n l bro id th i m d h compound 70 is then steam distilled until the oily layer is reduced to a of this invention correspondingto theiormula small fraction. The oil is then removed in a separatory 01111111 C2115 C2155; OiaHn funnel. The aqueous.solution containing the product "'N cflir lw weighs 352. parts and contains 2.0% chlorine (2.1%"

C "6,1 3 15 theoretical) and 0.84% nitrogen (0.80% theoretical).

The yield is therefore substantially quantitative. The s product corresponds to the formula 7 CH: OH:

I CHiCHaCHzCHaCHgHCHgCHrCH=CHCH2 05H; CzHs CHzOH=CHCHgCEaCHCHgGHzCHaCHzCH:

Cl C2 6 zHu 01 In a similar way, from 1,2-di-N,N-morpholinoethane and dodecenyl chloride, there is obtained the product of m z g g gg f gf gg z i gf igg gfig gi this invention, in aqueous solution, corresponding to the having the formula formula 7 Colin C 2H2: V

C H 01 01 CHI 6 N cmom N b I I/ \C1 C1/ NC:HaN

l I\ CH C H C H CH and from 1,3-dimethylamino-Z-hydroxypropane and ocn a u a a 5 s u o s tenyl iodide, there is obtained the compound having the in which said represents a dodecenyl group.

I OH: H: I

In the examples set forth above, sodium or potassium 5. As a new composition of matter, the compound iodide is employed in most instances. The results in all having the formula of these examples are satisfactory in the absence of sodium or potassium iodide, although somewhat longer 01 reaction times are generally needed to produce com- N-(hHs-N parable yields. The use of the stated iodide is a pre- Q E E ferred but not absolutely necessary condition.

I dam: in which said -C H represents a dodecenyl group.

1. As a new composition of matter, the symmetrical compound having the formula R1 El 40 6. As a new composition of matter, the compound having the formula in which the R groups taken singly represent alkyl groups of not over two carbon atoms and taken collectively rep- 5 in which said represants a dodecenyl group resent a divalent saturated aliphatic chain of four to five- As a new composition of matter the compound atoms which forms with the proximate nitrogen atom a having the formula fiveto six-membered heterocyclic monoamine group from the class consisting of morpholino, thiamorpholino, pyr- CH: 01 OH 01 CH; rolidinyl, piperidino groups and these groups having a lower alkyl substituent, R is an aliphatic hydrocarbon f l C s CnHu 01: CH:

group of eight to twenty carbon atoms having at least one bond of unsaturation, E is a member of the class consisting of alkylene, alkenylene, alkynylene groups in Which Said 1z 2s repl'esehts a dedeeehyl p; of two to four carbon atoms and a 2-hydroxypropylene A method the Preparation of a symmetl'leal group and X is an anion from the class consisting of eemPeulld having the formula chloride, bromide, iodide, sulfate, methylsulfate, phosphate, acetate, citrate, and tartrate. f

2. As a new composition of matter, the symmetrical Rr-N-E-N-Rr compound having the formula l x R; R: X

1 R! T 1; l in which the R groups taken singly represent alkyl groups of not over two carbon atoms and taken collec- X X tively represent a divalent saturated aliphatic chain of Whleh 1 18 an alkyl S P of he more than two four to five atoms which forms with the proximate nitroeal'boh atoms, 2 is alkehyl g p of eight to twenty gen atom a fiveto six-membered heterocyclic monocarbon atoms, E is an alkylene group of two to four amine group from the class consisting of morpholino, bon atoms, and X is a halogen having an atomic weight thiamorpholino, pyrrolidinyl, piperidino groups and these Of abo t 3 -5 to 12 groups having a lower alkyl substituent, R is an aliphatic A5 a new composition 0f matter, the compound hydrocarbon group of eight to twenty carbon atoms havhavlhg the formula 7 ing at least one bond of unsaturation, E is a member of CH; 01 01 OH; the class consisting of alkylene, alkenylene, alkynylene groups of two to four carbon atoms and a 2-hydroxypropylene group and X is an anion from the class conc CH! 15 sisting of chloride, bromide, iodide, sulfate, methylsuls atement iii fate, phosphate, aceta'te, citrate, and tar (rate, whichcomprises bringingtogether the compounds R] Br V at a reacting temperature in the range of about '25" C.

to the reflux temperature and thereby causing them to react in molecular proportions of substantially one of the former to two of the latter.

9. A method for the preparation of a symmetrical compound having the formula l a Rr-NENRt X Ra R: X

in which the R groups taken singly represent alkyl groups of not over two carbon atoms and taken collectively represent a divalent saturated aliphatic chain of four to five atoms which forms with the proximate nitrogen atom a fiveto six-membered' heterocyclic monoamine group from the class consisting of morpholino, thiamorpholino, pyrrolidinyl, piperidino groups and these groups having a lower alkyl substituent, R is an aliphatic at a reacting temperature in the range of about 25 C. V

to the reflux temperature and thereby causing them to react in molecular proportions of substantially one of the former to two of the latter. r

10. A method for the preparation of a symmetrical compound having the formula in which the R groups taken singly represent alkyl groups of not over two carbon atoms and taken collectively represent a divalent saturated aliphatic chain of four to five atoms which forms with the proximate nitrogen atom a fiveto six-membered heterocyclic monoamine group from the class consisting of morpholino,

- thiamorpholino, pyrrolidinyl, piperidino groups and these groups having a lower alkyl substituent, R is an aliphatic hydrocarbon group of eight to twenty carbon atoms having at least one bond of unsaturation, E is a member .of the class consisting of alkylene, alkenylene, alkynylene groups of two to four carbon atoms and a 2-hydrox propylene group and X is an anion from the class consisting of chloride, bromide, iodide, sulfate, methylsulfate, phosphate, acetate, citrate, andtartrate, which comprises bringing together in the presence of an inert volatile solvent and a polar iodide soluble in the reaction mixture the compounds at a reacting temperature in therange of about 25 C. to the reflux temperature and thereby causing them to react in molecular proportions of' substantially one' of the former to two of the latter.

. "a 11. A method for the'preparation of the symmetrical compound having the formula x in Ba x in which R is an alkyl group of. no more than two carbon atoms, R is an alkenyl group 'of "eight to twenty carbon atoms, E is an alkylene group of two to four carbon atoms, and X is a halogen having an atomic weight of about 35.5 to 127, which comprises bringing together in the presence of an inert volatile solvent at a reacting temperature in the range of about 50 to 125 C. to the reflux temperature and thereby causing to react in molecular proportions of substantially one of the former to two of the latter the compounds EN/ R1 R1 and R X.

12. A method for the preparation of l C(aCrzHzs 0121123 CH3 which comprises bringing together in the presence or an inert volatile solvent at a reacting temperature inv the range of about 25 C. to the reflux temperature and thereby causing to react in molecular proportions of substantially one of the former to two of the latter N,N- tetramethylethylenediamine and dodecenyl chloride.

13. A method for the preparation of which comprises bringing together in the presence of an inert volatile solvent at a reacting temperature in the range of' about 25 C. to the reflux temperature and thereby causing to react in molecular proportions of substantially one of the former to two of thelatter N,N'- tetramethylbutylenediamine and dodecenyl chloride.

1 4. A method for the preparation of CH: 01 V (ll/CH3 NCHr-CEC CH2 Ha 12 2: l2 23 which comprises bringing together in the presence of an inert volatile solvent at a reacting temperature in the P range of about 25 C. to the reflux temperature and thereby causing to react in molecular proportions of substantially one of the former to two of the latter 1,4- bis(dimethylamino)-2-butyne and dodecenyl chloride.

15. A method for the preparation of References Cited in the file of this patent UNITED STATES PATENTS 2,271,378 Searle Jan. 27, 1942 2,287,465 Boch June 23, 1942 2,375,853 Kirby et a1. May 15, 1945 2,525,777 De Benneville Oct. 17, 1950 (Other references on following page) 11 12 UNITED STATES PATENTS Letovsky: Czech. Chem. Communs, vol. 15, pp. 406- 411 (1950). V r B: 82:: gig Chem. Abst. 47:107550 (Elliker); 47:12673ad. (Spur Szabo et a1. Feb. 1953 and Minor); 46:684hi, 685a (Resuggan, Alia, and Reynolds et a1. Aug 1955 5 Mueller et a1.); 46:5659; 5660a (Chaplin).

Stewart: Soap and Sanitary Chemicals, April 1950, PP- OTHER REFERENCES 124-127. v

Linsker et al.: m.c.s., vol. 68, pp. 1432 (1946) UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION paient o, 2,933 529 April 19, 1960 Jesse C. H. Hwa

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 7, line 53, column 8, line 71 and column 9, lines 26 and 59, after "unsaturatiomfl each occurrence, insert from the class consisting of alkenyl, alkdienyl alktrienyl, and alkynyl groups, same column 9 lines 3 to 7 the formula should appear as shown below instead of as in the patent:

N-E-N and R X Signed and sealed this 20th day of September 1960,

(SEAL) Attest:

KARL H. AXLINE ROBERT C, WATSON Attesting Officer Commissioner of Patents UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 2,933,529 April 19, 1960 Jesse C. H. Hwa

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 7, line 53 column 8, line 71 and column 9, lines 26 and 59, after "unsaturationfl' each occurrence insert from the class consisting of alkenyl, alkdienyl alktrienyl,- and alkynyl groups, same column 9', lines 3 to 7, the formula should appear as shown below instead of as in the patent:

N E N and R1 R1 Signed and sealed this 20th day of September 1960.

(SEAL) Attest:

ROBERT C WATSON KARL H. AXLINE Commissioner of Patents Attesting Officer

Claims (2)

1. AS A NEW COMPOSITION OF MATTER, THE SYMMETRICAL COMPOUND HAVING THE FORMULA

3. AS A NEW COMPOSITION OF MATTER, THE COMPOUND HAVING THE FORMULA