US2676955A

US2676955A - Urea adducts of quaternary ammonium compounds

Info

Publication number: US2676955A
Application number: US191504A
Authority: US
Inventors: Alfred W Weitkamp; Jerome W Arkis; George W Flint
Original assignee: Standard Oil Co
Current assignee: Standard Oil Co
Priority date: 1950-10-21
Filing date: 1950-10-21
Publication date: 1954-04-27
Anticipated expiration: 1971-04-27

Description

Patented Apr. 27, 1954 .asmisa ADDUQTS o 'AMMONIUM CO Alfred W. Weitkam'p, Lansing, .rIll., .Jemmei W.

-1 This invention relates to quate gnary 11111119- nium compounds." More specifically; it relates to a novel series of chemical compounds composed where thesubstituents onthe nitrogen atomq p "f: i fierfef t organic fadicals and X represents .an anion. jT hese' terials' are 'knownto be useful in various .iie1ds,..d l! ndi upon the specific substituents contained" therein. They have beeniusedy-for. exam legas germicides, fungicides, surface-active ,agents, ,therapeutic agents, and the like. 'Tl'i'eir utilization"hasbeen handicappedl liowever, otvinto -the fact that dia au highl i sqepi ,imaierialsa- -ar therefore obtained, sticlgypnp'astyme lid ree -sta w i ie enq tqiseqv re iizha aquat rmr ammonium compounds of.

tam .class can .pe

muls ofi w' ih eure ube n inondonic;.;-do .no -interiere gyvithithe, characteristic, activity ,.of..-..the I aquaternary. ammonium.saltrfonexample, surface lactivitywor. :fungicidahoi. gennicidal lcharater) sses,'".wlfiich.;aiie"d1fiicult,.to.measura h mile, r

" H ...elass awardin tomcthods.describedin theprior tareeeafil -p eka me s bl nde ;andiciis' e iai .-t fireerfl w n n udery- 32 "The... surface .actiuity...of the "quat rn r BR 111 0- .nium ...oom15.ound...i:leduces'.' the .surface .tensionam aqueous solutions of the adduct, and facilitates .spreading-andlpenetration of. the .urea .in, certain applications. All of..these. advantages .replffifient .,Sl1'iking, improvements .over ithe, quaternary .ammoniumicompoundsnof the .priorgart.

One,..o,bject,. of .burdnventionis to .convert quasternary ammoniumsomnoundsfinto. a. ,form. more readily and conveniently stored, handled,.measiuredhandrapplied. ,.-Another. o.bject. is. to .convert urea intoqa more effectiyelyi utilizable; form. .An- .other obj ectis to preparaachemical.combination .of .urea. and ,aquaternary ammonium. compound having, synergistic properties, as ainutrientland .,an. antibiotic ,wheriLemployed in,.p,1ant sprays. iA Jurther. obiectis to, separate quaternary ammo- .nium. compoundsintonlasses according, t o,.strucituralhconfi ration. .-.-Other.,objects..of ,ounimzen- .tionmillebe.apparent-front.thefiqescription. thereioiianitheannendednlaims.

;The..pneparation ,of our ..new .sompositions .of amattenisicarried ,out, by.,reacting nreawitha .qua-

ternary ammonium compound ..of .our -.defined The qua ernary vammonium compound preferably dissolved in n, organic liquid, which serves as a diluent to produce a solution of low iyiscgsi yman h resultin s luti n s cont c i s re l d' ureatsplxentata temperatur hetwee gah g lan fi ir -e i ferab b twe n ,,.,a!gout}2 au ifi unt lh re ct on i mmb re .Jnarea tiszup q c s a l oithe ired urea dduct in -the, diluent liquid. The 1 w;v i ub. .edat ifiltr tiq s tli nd-demother liquor, erefrom. The ..wasl1ed @Qsdllil Th idrn olid -the.new...comon ...-Q: Y! iT i9. su table wi hout iure 11 eatme efonthamany.uses tmwhich itis damnedsuitaule d iluents i for the quaternary ,ammo- ,mum.lqompoundsainclude methanol, ..ethanol,.. n- ..propyl alcohol, ,isoprppyl, alcohol, n-.butyl alcohol, .k .yle ..s1x, .o an he like --These solvents .afumti nas multan ously to. .diss lr th quater- 50 nary-ammonium compounds. and--reduce. the. viscosity thereof, ar d to a tiuate the urea for adduct formation.

. "effor complete-reactioniof .thenuaternary vam- .moriium.compound i ith'urea. the ratirfof urea fifi'litdllquateriiary fainmonium eompoundlshouldbe ep etalpnd ril bet ee abou m a 2 ho rs.

at least one mole of urea per methylene group in the straight-chain organic radicals containing more than 5 methylene groups which are attached to the nitrogen atom. When substantially pure adducts are desired, uncontaminated with free urea, a smaller ratio of urea should be employed.

It will be apparent that numerous variations of the above procedure may be employedfor making our new compositions. The following variations are illustrative:

1. The quaternary ammonium compound in excess is stirred at room temperature with a saturated solution of urea in a urea solvent, such as a lower aliphatic (C1 to C6) alcohol. The ad duct that precipitates is filtered off, washed with a low-boiling solvent such as acetone or ether, and dried. The unreacted quaternary ammonium compound in the wash liquor is recycled.

2. Theoretical proportions of urea and the quaternary ammonium compound are dissolved in a lower aliphatic alcohol, and the solution is spraydried.

3. A concentrated solution (for example, 50 to 75 percent by weight) of the quaternary ammonium compound in a lower aliphatic alcohol is mixed with the theoretical proportion of dry powdered urea, the mixture is stirred until it becomes homogeneous, and the resulting slurry is dried.

4. An unsaturated alcoholic solution of urea and a quaternary ammonium compound in approximately theoretical proportions is diluted with an organic liquid which functions as an alcohol solvent and a urea-adduct antisolvent. F

Example I Ten grams of a '75 percent by weight solution of dimethyldilaurylammonium bromide in isopr'opyl alcohol was mixed with a saturated solution of urea in methanol containing ten grams of urea, the mixture was agitated approximately minutes at room temperature. The reaction mixture was then diluted with 50 milliliters of diethyl ether and was filtered. The solids were washed with an additional quantity of (iiethyl ether and were dried in air. The resulting product was a fine White powder containing 5.25 percent by weight of bromine. This corresponds to a ratio of one mole of the quaternary ammonium salt to 17.6 moles of urea, or 33 percent by weight of quaternary ammonium salt in the urea adduct. Fungicidal tests on the adduct revealed that its fungicidal potency against Sclerotz'm'a fructz'cola was exactly proportional to the content of quaternary ammonium salt, the MLD-SQ being obtained at a concentration of 2.8 milligrams of quaternary ammonium salt per liter, and MLD95 at 5.9 milligrams per liter.

Example II inisopropyl alcohol was treated as described in Example I with ten grams of urea in methanol. The resulting white powder analyzed 4.15 percent by weight chlorine, corresponding to one mole of ammonium salt per 8.6 moles of urea, or 40 percent by weight quaternary ammonium salt in the adduct. Consistent with this ratio, the fungicidal MLD- against Sclerotima fructicola was obtained at a concentration of 1.7 milligrams of quaternary ammonium salt per liter, and the WILD-95 at 2.4 milligrams per liter.

Example III Urea adducts were similarly prepared from the following quaternary ammonium compounds:

Benzyldimethyllauryloxymethylammonium chloride. Benzyldimethyllaurylthiomethylammonium chloride. Lauryltrimethylammonium chloride.

The quaternary ammonium compounds from which our novel compositions are derived are substituted dimethylammonium compounds having the following structural formula,

where R and R comprise at least one straightchain organic radical containing at least five methylene groups, where R. and R together contain not more than one carbocyclic-substituted aliphatic radical, said carbocyclic-substituted aliphatic radical containing not more than six carbon atoms in the ring, and where X represents an anion, such as halogen, sulfate, hydroxyl, or nacyloxy group. The said straight-chain group may be n-alkyl, n-alkenyl, n-alkynyl, n-alkadienyl, n-oxaalkyl n-polythiaalkyl, and the like, where m and n represent zero or positive integers which must total at least five, and where X represents halogen. The urea-reactivity of the straight-chain organic radical is not afiected by the substitution thereon of hydroxyl or fluorine in any position, or by substitution thereon of other halogen, amino, or mercapto in the omega position. The carbocyclic group may be cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl, and the like, and may contain a halogen, hydroxyi, or mercapto substituent in the para position. The most useful group of our new compositions which we have so far prepared are obtained from quaternary ammonium salts containing one or two Clo-C20 n-alkyl groups. These compounds have excellent germicidal, fungicidal, and surface-active properties, which are retained and improved when the compounds are reacted with urea.

Our new compositions are useful in a wide range of applications. They may be used as a combination plant food and fungicide for fruit trees and plants in general. For this purpose, they can be conveniently used as a dust, owing to the fact that they are free-flowing, non-hygroscopic powders; and they can conveniently be combined with insecticidal agents and inert materials which are commonly applied separately.

Since garden crops or ornamental plants are commonly dusted in the morning when the plants are wet with dew, the use of our new compositions or materials comprised thereof at such times is distinctly advantageous, permitting rapid decompositionof the urea adduct and immediate feeding and fungicidal action by the urea and the quaternary ammonium salt. Alternatively, our new compositions can be used advantageously as a component of sprays for plants and trees. In this connection, the surface-active characteristics of the quaternary ammonium compounds are highly advantageous. When the adduct'is added to water, it decomposes, yielding a solution which has a lower surface tension than a comparable urea solution and for this reason being more capable and eificient in feeding nitrogen to plants. If a higher ratio of urea is desired, an additional quantity of urea can be blended with theadduct, owing to the powdery form of the latter. Our new compositions are also useful in pharmaceutical preparations, for example in mouth washes, tooth pastes, and the like. They are especially useful in tooth powders, where their non-hygroscopic nature is essential, and where their combined germicidal and ammonia-producing actions are highly desirable. Many other uses will be apparent to those skilled in the art. f"

While we have described our invention. in connection with certain specific embodiments thereof, it is to be understood that we are not limited thereto. The compositions of our invention are new and useful broadly within the scope of the disclosure thereof, and it is further to be understood that any modifications or equivalents that would ordinarily occur to one skilled in the art are to be considered as lying within the 'scope of our invention.

In accordance with the foregoing description, we claim as our invention: -j

1. An adduct of urea and a quaternary dimethylammonium compound having as substituents on the nitrogen atom thereof (1) at least one straight-chain organic radical containing at least five methylene groups and (2) an aliphatic radical containing not more than one carbocyclic-substituent, said carbocyclic substituent containing not more than six carbon atoms in the ring, said quaternary dimethylammonium compound being otherwise free from functional groups reactive with urea.

2. The composition of claim 1 wherein said quaternary dimethylammonium compound has as substituents on the nitrogen atom thereof at least one C:C2o n-alkyl radical.

3. The composition of claim 1 wherein said quaternary dimethylammonium compound has as substituents on the nitrogen atom thereof at least one n-oxaalky radical containing at least five methylene groups.

4. The composition of claim 1 wherein said quaternary dimethylammonium compound has as substituents on the nitrogen atom thereof at least one n-thiaalkl radical containing at least five methylene groups.

5. An adduct of urea and a quaternary dimethylammonium compound having as substituents on the nitrogen atom thereof (1) at least one straight-chain organic radical containing at least five methylene groups and 2) an aliphatic radical free from cyclic substitutents, said quaternary dimethylammonium compound being otherwise free from functional groups reactive with urea.

6. An adduct of urea and a dialkyldimethylammonium compound wherein at least one of said alkyl radicals is an n-alkyl radical containing at least six carbon atoms.

7. An adduct of urea and a dialkyldimethylammonium salt wherein at least one of said alkyl radicals is an n-alkyl radical containing at least six carbon atoms.

8. An adduct of urea and dimethyldilaurylammonium bromide.

9. An adduct of urea and benzyldimethyllaurylammonium chloride.

10. An adduct of urea and benzyldimethyllauryloxymethylammonium chloride.

11. An adduct of urea and benzyldimethyllaurylthiamethylammonium chloride.

12. An adduct of urea and lauryltrimethylammonium chloride.

13. In a method for separating quaternary dimethylammonium compounds according to structural configuration from a mixture thereof, said mixture comprising a quaternary ammonium compound (I) having as substituents on the nitrogen atom thereof (1) at least one straightchain organic radical containing at least five methylene groups and (2) an aliphatic radical containing not more than one carbocyclic substituent, said carbocyclic substituent containing not more than six carbon atoms in the ring, said mixture further comprising at least one quaternary ammonium compound (II) of another type, and said mixture being substantially free from components containing functional groups reactive with urea, the steps which comprise contacting said mixture With urea and a urea solvent and separating from the resulting reaction mixture a solid, non-hydroscopic adduct of urea and said quaternary ammonium compound (I), substantially free from said quaternary ammonium compound (II).

References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 2,346,632 Wolfert et al Apr. 11, 1944 2,518,677 Garner et al Aug. 15, 1950 2,541,248 Hibbs Feb. 13, 1951 FOREIGN PATENTS Number Country Date 443,795 Great Britain Mar. 6, 1936 OTHER REFERENCES Lawrence, Quaternary Ammonium Germicides (Academic Press, New York), 1950, pp. 24-28. (Copy available in Pat. Off. Scientific Library.)