'Uni'ted'states Patent Office
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amino“. 5, 1943' l ‘ 2,331,276 .. 'UNI'TED‘STATES PATENT OFFICE CYANATES AND PROCESS OF PREPARING THE‘ SAME ‘ Jose: rm, Pitman, N. J. , assignor to E. I. in Pont de .Nemours & Company, ' Del, a corporation of Delaware 7 on, No Drawing. Application October 30, 1940, Serial No. 363,524 ' 12 Claims. (CI. 260-4025) 'This invention relates to novel organic com other alkyl groups, or by alkyloxy, alkylamino, pounds and to a process for preparing the same. or acyl imino groups, having an alkyl chain of . More particularly this invention deals with-novel from 9 to 36 carbon atoms, while the thiocyanate thiocyanates and isothiocyanates obtainable by radical -—SCN, may be replaced by the isothio condensing a salt of thiocyanic acid with halo cyanate radical, -—NCS; geno-methylam'ides having long-chain alkyl radi These compounds are prepared, according to cals in their structure. this invention, by reacting with a salt of mm It is anobiect of this invention to prepare novel 'cyanic acid, for instance an alkali-metal thic organic compounds which are useful in the art cyanate or a heavy metal thiocyanate, upon an ‘ of treating textile ?ber, especially for the pur 10 amido compound of the general formula pose of endowing the same with water-repellency or with softness of feel. Further important ob R——Y—1?'—CHz—-X- ' jects of this invention will appear as the descrip I , - R’ . tion proceeds. wherein R, Y and B.’ have the same significance The novel compounds of this invention are 15 vas above, while X stands for halogen,‘ preferably characterized by a structure corresponding to the ‘chlorine or bromine. , following general formula At first‘ a thiocyanate is formed, which how ever in most cases rearranges gradually to give the isothiocyanate. Taking stearamido-methyl I 20 chloride and potassium thiocyanate as conven - wherein R is an aliphatic or alicyclic radical (in ient individuals for the purpose of illustration, other words, a non-aromatic radical) containing. the reactions may be expressedby the following at least 7 carbon atoms and, being free from equations: . water-solubilizing groups. Y is a link selected .from the group consisting of C0,, 0,-CO, 25 NH-CO, CO-NHCO and O-GO-NHCO; R’ stands for hydrogen, a lower alkyl-group, or a lower alkylene group which is attached to the nitrogen atom of another radical of the form At room temperature, the rearrangement is 30 very slow and may take several weeks for com ‘ R-Y-IlI-CHr-Q plete isomerization. But by heating to conven (R, Y and Q having the same signi?cance as ient temperatures, say up to 100° C., the process above) ; and ?nally, Q stands fora radical of the may be completed within a few hours. group consisting of the thiocyanate radical 'The ease with which the chloromethyl com --S—CN and the isothiocyanate radical --N—CS. ,- pounds react with the salts of thiocyanic acid As typical illustrations of compounds falling 7 depends greatly upon the content of moisture of within the above general class may be mentioned , the‘ reaction mass. If the metal thiocyanate con ‘ at this point: tains a small amount of moisture, that is from 2 Stearamido-methyl-thiocyanate: ‘ to 5% by weight, the reaction proceeds readily 40 at room temperature and is ?nished in several Ci7I'I35—CO—-NH—CH2——SCN , hours. If the reaction medium is perfectly dry no noticeable reaction takesplace at ‘room tem N-methyl-stearamido-methyl-thiocyanate: perature, but a higher temperature such as 60 CnHas-C0—N—CH:—SCN . to 100° C. is necessary to bring the reaction about. Ha ' ‘ 45 The reaction is usually carried out in an inert and medium such as benzene, carbon tetrachloride, cyclohexane, trichloroethylene or ethyl acetate, ' Methylene-bis(stearamido-methyl-thiocyanate) : ' but it may also be carried out in the absence of a solvent by simply heating the chloromethyl amide '50 with a salt of thiocyanic acid and then separating ' the inorganic salts from the reaction mass by a suitable solvent or by ?ltration at a temperature My invention, however, is not limited to these above the melting point of the reaction product. compounds, since it embraces compounds wherein This ‘reaction may also be carried out under the group CnHas above is replaced by ‘various at vacuum if the reaction products are, not volatile. 2 2,331,276 ‘ The amount ' of- the salt of thiocyanic acid and similar compounds derived from other higher necessary to carry the reaction to completion may fatty acids or alcohols, whether saturated or un be one mol equivalent per mol of the chloro saturated, straight-chain or alicyclic, (for in methyl derivative or in excess thereof, as there stance naphthenicand 'hydroabietic), and which ' _ is no difficulty involved in separating the organic are generally. derived from the constituents of thiocyanate from the inorganic salts. A large natural oils, fats and waxes. ~ ' excess of inorganic thiocyanate may be used. The chloromethylene derivatives of these‘ In the reaction between the organic methylene amides are usually low melting solids which are chloride and the inorganic thiocyanate, any very soluble in solvents like benzene or carbon residual acidity left in the product or occluded 10 tetrachloride. They may be prepared as de therein may be eliminated by carrying out the re scribed in the above mentioned patents by react action in the presence of a small amount of a ing the amide with gaseous hydrogen chloride and basic reagent like sodium'carbonate, barium car paraformaldehyde, or by using an aqueous form~ bonate, magnesium oxide», or pyridine. The addi aldehyde solution and hydrogen chloride gas, or tion of these products tends also to decrease the even by using aqueous formaldehyde and aqueous formation of by-products. "When the reaction is hydrochloric acid. In this latter case it is, how complete, it is desirable to~ neutralize any free ever, advisable to use some calcium chloride or acids which may remain in'the‘ reaction product another water removing agent together with the by stirring the product with a slightly moist basic formaldehyde and hydrochloric acid. The chloro material like potassium carbonate, calcium oxide 20 methylene compounds may also. be prepared by or magnesium oxide. In this way a product can the action of hydrogen chloride on the correspond-v be obtained which is neutral to Congo red paper. ing methylol amides. ‘ The last traces of moisture may be removed by After the preparation of the chloromethyl com ' treatment with some 'drying agents like CaClz, pound, the excess of hydrogen chloride is re moved either by evaporating the solvent in vacuo sodium sulfate, or alumina. The initial methylene halide compounds em or byblowing an inert gas like'COz or N2 through ployed in my invention maybe selected from the solution until all or most of the HCl is re among any of the compounds described and moved. In view of the slow process of isomerization, claimed in U. S. Patent No. 2,131,362, or in the products of this invention are generally prob British Patents Nos. 492,699, 494,761 and 501,480, 30 ‘ and may be prepared by the methods therein set ably mixtures of thiocyanates and isothio forth. Generally speaking, these compounds are cyanates, whose exact composition varies with prepared by reacting with formaldehyde and hy _ the age of the product, and whose properties are drogen chloride on an amide compound of the a composite ‘result of the properties of the indi general formula R—Y—-NH-—R', wherein R, Y vidual components and their relative proportions and R’ have the same signi?cance as above, it be at any given time. ing noted that Y always contains a CO group next ' The pure thiocyanates, which may be approxi to the NH, thus placing the compound in the mated by the products of this invention as fresh classification of amides. As typical illustrations ly prepared, are generally oils or low-melting of such amide initial material, without however 40 waxes, soluble in benzene and other common or any intent to limit this invention, may be men— ganic solvents. They react readily with tertiary bases to give crystallizable, water-soluble com tioned: pounds, presumably quaternary ammonium com Stearamide: pounds, thus: ‘ ' C1'zI-h5—CONH2 45 \Octad'ecyl-carbamate: C1sI‘Is'r-O-'—CONI-I2 Octade cyl-urea : 50 ‘ C1sH31-—NH-CO—NH2 Stearyl-urea: - CrvI-Isa-CONH-CO-NH: Octadecyi-allophanate: . 55 The quaternary compounds are stable both C1aH3v—-O-—CONH—-CONH in substance and in aqueous solution, and no Methyl-stearamide: ' longer isomerize into isothiocyanates. They are CrzI-Ias-C ONH-CHa also solublein organic solvents, and concentra Distearamido-methane: tions' thereof up to 50% by weight may be readily 60 CnHaa-C ONH prepared. When cotton fabric is treated with an aqueous solution (0.2 to 2%) of these quater H: nary compounds and then ‘dried and baked in the _ ‘ CnHas-C 0111K absence of moisture at a temperature between 100 Montanic acid amide: and 170° 0., it acquires a soft feel and a high de 65 gree of water-repellency, both of which proper ties are permanent to laundering and dry-clean 2-hexadecyl-eicosanoic acid amide: ing. Smaller concentrations, say 0.01 to 0.2% are CmHar-CIEL-C ONH: su?icient to impart softness to fabric under the . mHza same treatment. - 70 Similar effects upon fabric may be obtained by Tiidecamethylene-diamide: - similar treatments using the thiocyanates them - 0 ONE: selves from organic solution, for instance ben (0112)“ zene, trichlorethylene or carbon tetrachloride. 0 ONE: 75 The pure isothiocyanates, which may be ap 2,331,276 , 3 proximated by the products of this invention after When applied to cotton and rayon ta?'eta from standing for‘ several months, are likewise oils or a 1%.solution in benzene and then subjected to , low melting waxes.