Патент USA US2128887код для вставки
Patented Aug. 30, 1938 2,128,887 UNITED STATE"-S are TENT Bowl-cs 2,128,887 "PRODUCTION »OF SATURATED‘ MORPHO ' :LINE ALKANOL-ALKYL ETHERS ‘Alexander L. Wilson, .PittsburghaPanr assignonlby mesne assignments, to UnionOarbide and Car ‘bon’Cjorporation, a corporation of‘New'Yoi‘k No Drawing. Original application December 4, “1934, Serial No. 755,9 12. . ‘Divided and thisap ‘ V plication ,May 5, 1937, Serial No. 140,837 5 Claims. (Cl. 260-247) This invention relates to ‘the production of and each R represents either hydrogen or \the morpholine'ethanolsand certain of their ethers. same or- a di?erent alkyl group: ‘One modi?cation of the invention concerns the production of the said compounds by a process I. (a) 2XCHR—OHR—O—CHR—CHRX+4NH: :aqua or alcohol a B5’ dihalogeuated dialkyl other ,5 thatinvolves reacting a. '13s’ dihalogenated dialkyl ether'with ammonia in aqueous or alcoholic solu tion, or-With morpholine or a substituted mor pholine in an alkaline vmedium. The resultant reaction pro-ducts .are heated and reacted with a N H alkaline A o/ ‘_ o+nHx ‘\onn-onn/zéonnfona/ an’ excess of morpholine with or without diluent ride or intermediateproduct, azstrong base such 410 ‘CHE-"OER a ,dimorpholinium halide '15 ‘or, as in the reactionroftmorpholine with di ‘as- sodium-hydroxide isrrequired. . ‘ solution ‘;1.0 ?xed alkalisuch as caustic soda, preferably in ‘excess. The reaction mixture must be maintained alkaline-during the ?rst step of the process either :by the use .of an excess .of ammoniacal solution, chlordiisopropyl ‘tether, why caustic ‘alkali. For ‘the decompositionlof ‘the dimorpholinium chlo ———-—> GHR—Q HR II. OHR-—OHR 21:15 can-‘one 0. (+Na0H hot) \ —————) ' When in the ‘process, p5’ dichlordiisopropyl ether is reactedwith-morpholine, there is pro duced as at'?nal :product, dimethyl morpholine ethanol, which is a stronglyrbasic water-soluble amine boilingat 230?’ C. ‘under. atmospheric pres z25 sure. i :25 ‘According ‘to zanother ‘modi?cation of the .in 'vention, a vinyl ether of 1a morpholine ‘ethanol, ‘which may be produced in a manner described ; $30 above vin the process of producing ~morpholine ~~ethanol, or in other ‘suitable manner, is hydro lyzed and converted‘ to 'a'morpholine ethanol by acidifying the said ether inaqueous solution fol lowed "by a treatment of the resultant product 9,5 with a‘strong ‘base, such as sodium hydroxide. Thus itis possible to securev Very high yields ,of morpholine ethanol from (the dihalogenated di alkyl ether used as starting material. The morpholine 'alkanol-vinyl ethers produced H4“ in the ?rst step of the process further may be convertedvto saturated morpholine alkyl ethers by ‘the catalytic vapor phase hydrogenation ‘thereof‘at temperatures somewhat above the boil ingipoint of the morpholine alkanol alkyl ether ' being‘produced. The liquid condensate from the ‘ hydrogenation is then boiled with aqueous min eral acid or the equivalent’to decompose any un reacted morpholine alkanol vinyl ether, follow ing' which an excess of sodiumphydroxide is added 7:50 and the amine layer which then separates is fractionally distilled. The type of reactions in volved in the various steps of this invention is illustrated by the following equations, in which X stands, for any halogen, n=either 42 or 4, 7-30 >N——CHR—CHRO OHzGHz one-011R - a morpholine alkanol ethyl ether The followingvexamples. serve .to ‘illustrate ‘the invention: ‘ ' _ ‘ Example ‘1 A mixture of 83 pounds 5,6’ dichlordiethyl ether, 176 pounds of water and 98 pounds of 40 ammonia was reacted to completion .in an .agi tated closed vessel during a period of four to ?ve ‘hours at a‘temperature within the range from 65° to 80° C., and under a pressure rang ing vfrom 45 to 75 pounds per square inch gauge. 45 The reaction product was cooled to around 40° C., and was then treated ‘with a- slight excess of sodium :hydroxide. ‘The ammonia,tfree low boiling amines, and water vwere then distilled from the mixture, leaving‘ behind a residue 'rof sodium chloride containing ‘the ‘less volatile amines. These latteramines :wereextractedfrom the sodium chloridewith-benzeneandiwere added to the distillate. Refractionation of, this :faug pmented distillate -then yielded ,successive time 2,128,887 sodium hydroxide was ‘then added whereupon the ture of water and morpholine ethanol vinyl liquid strati?ed, forming an amine layer which ether, morpholine, and morpholine ethanol. The was separated and was fractionally distilled. The fraction thereof distilling within the range morpholine ethanol vinyl ether fraction, boil of from 204° to 206° C. and containing mor ing at 209° to_211° C., and the fraction con taining morpholine ethanol and boiling within pholine ethanol ethyl ether, was separately re the range 'from'2l5° to 235° C., were separately‘ covered, and represented a yield of 61% based recovered. In this example ammonia and di-, upon the original morpholine ethanol vinyl ether . chlordiethyl ether were employed in the molar reacted. It will be understood that although reference 10 10 ratio of 10 : 1. ' The molar ratio of ammonia to dihalogenated is made herein to distillations of the various re dialkyl ether may vary between rather wide action mixtures under atmospheric pressure, it is readily possible, and under some conditions limits, ranging from around 2 : 1 to a ratio of desirable, to conduct these distillations under 20 or more to 1. In general, the yield of mor subatmospheric pressures, in order to secure the pholine alkanol vinyl ether increases as. the am usual advantages of reduced distillation tempera monia to dihalogenated dialkyl ether decreases, tions containing ammonia, a constant boiling mix- ' tures and protection against heat decomposition of the compounds present. and the maximum obtainable yield of morpho- 7 line ethanol increases similarly. . As shown in the various examples, the free Other Be’ dihalogenated dialkyl ethers may be 20 substituted for that speci?cally named in the foregoing example. Moreover, it is possible to substitute morpholine for the ammonia in the ?rst stage of the process, as indicated by the following example: v amines may be obtained from solutions of their 20 hydrochlorides by treatment with less volatile bases. In the case of sodium hydroxide, this may ‘be added in the combining proportion, Volatile amines distilled off, the higher-boiling amines ' ~ extracted from the residue with alcohols, such as isopropanol, and the amines recovered. Y Example 2 on the other hand, an excess of sodium hydroxide may A mixture containing 1/2 mol each of 55’ di chlordiisopropyl ether, morpholine, sodium hy ' be used, volatile amines distilled'off, and the droxide and water was charged into a ?ask under P30 reflux and was reacted at the boiling point for ?fteen hours with the addition of suf?cient water to keep in solution the sodium chloride produced. The reaction product then'was distilled, and un reacted ether and morpholine thus removed. 1135 The residue, containing salt and amine hydro higher-boiling amines,’ or both the latter and-the volatile amines present prior to the distillation, may be decanted or extracted from the caustic layer with a volatile solvent such as benzene. Other means than those speci?cally described may be used for recovery of the desired amines. v_ Thus, the reaction mixture from the ammonia " 35 dichlorethyl ether reaction maybe concentrated chlorides, was evaporated to dryness and ex and unreacted materials‘ removed,‘ followed by a tracted with isopropanol, thus throwing out the fractional crystallization 'of the amine hydro sodium chloride. The extract, upon evaporation ' chlorides, and a treatment with caustic alkali of yielded dimethyl dimorpholinium chloride in the the appropriate crystalline fraction; or the said form of a stable white salt of high~melting point, reaction mixture may be concentrated, and then soluble in water and in alcohols. This salt was heated with'an excess of alkali, thus forming a heated to 150° C. with a strong hot aqueous solu layer of mixed amines. This amine mixture then tion of sodium hydroxide, yielding an _oil layer may be- fractionally ‘distilled, and the various insoluble in the sodium hydroxide but soluble in amines recovered. 45 . 45 benzene. A benzene extract of this layer wasi Although the reaction between the dihalogen distilled, and an amine fraction boiling at 220° ated ethers and ammonia may be conducted at to 225° C. under atmospheric pressure was sep pressures around atmospheric, it is preferable to arately recovered. This corresponds to di use low superatmospheric pressures in order to methyl morpholine ethanol vinyl ‘ether, and was 'eifect the most eflicient operation; and pressures a strong base, soluble in benzene and alcohols, up to 100 pounds per square inch gauge are par and less than 1% soluble in water. ticularly satisfactory. ' The intermediate product or morpholine al The morpholine alkanol alkyl ethers prepared kanol vinyl ether formed in the ?rst stages of the in accordance with the invention are excellent process, is readily convertible to the correspond high-boiling solvents for gums; resins, such as 55 vinyl resins; and cellulose derivatives. They also ing saturated morpholine ether, such as, for ex ample, morpholine ethanol ethyl ether, by a are useful as reaction solvents in Grignard syn— theses andv reactions involving the liberation of vapor phase catalytic hydrogenation, as illus acid, in acetylations with acetyl chloride, and in trated below. ' ' dehydrohalogenations. They may be used in > Example 3 (El) preparing volatile emulsifying agents and mer A reaction tube of a well known heat-resistant cerizing penetrants, and in dyeingoperations. glass was ?lled with chips of a porous arti?cial The term “a morpholine ethanol alkyl ether” ?lter stone essentially consisting of silica that and similar terms appearing in the speci?cation had been impregnated with a mixture of nickel and claims are intended to ‘designate not only 65 andthorium oxides which then were reduced morpholine ethanol alkyl ether per se but also with hydrogen. Through this catalyst cham substituted morpholine ethanol alkyl ethers, such as dimethyl morpholine ethanol ethyl ether. This application is a division of my copending of‘ hydrogen and morpholine ethanol vinyl ether vapor in the ratio of '4 to 5 mols of hydrogen application, Serial No. 755,912 for U. S. patent, 70 per ‘mol. of the ether. The resultant vaporsrwere ?led December a, 1934, entitled “Production of condensed at 20° C., yielding a liquid, which then . morpholine ethanols and certain ethers thereof.” It will be understood that the invention is not was boiledwith an excess of dilute aqueous hy ber heated at 200° to 250° C. was passed a stream drochloric acid, thereby decomposing unreacted morpholine’ ethanol vinyl ether. An excess of limited by the speci?c disclosure appearing in the examples, but that on the contrary it is sus 75 3 2,128,887 ceptible of modi?cation within the scope of the sure containing the morpholine ethanol ethyl appended claims. ether. ' I claim: 1. The process of making a morpholine ethanol ethyl‘ ether, which comprises hydrogenating a morpholine ethanol vinyl ether in the vapor phase in the presence of a hydrogenating catalyst. 2. The process of making a morpholine ethanol ethyl ether, which comprises hydrogenating a 10 morpholine ethanol vinyl ether in the vapor phase in the presence of a hydrogenation catalyst, treat ing the resultant reaction mixture near the boil ing temperature with aqueous acid solution, re acting this mixture with an excess of strong 15 alkali, thereby effecting strati?cation of the mix ture into a plurality of layers including an amine layer, separating the amine layer from the re ‘ 4. The process of making a morpholine ethanol ethyl ether, which comprises hydrogenating a corresponding morpholine ethanol vinyl ether in the vapor phase, heating the reaction mixture with a dilute mineral acid, thereby decomposing unreacted morpholine ethanol vinyl ether, react ing the resultant mixture with an excess of a strong base, thereby stratifying the mixture into 10 a plurality of layers including an amine layer, i’ractionally distilling the said amine layer, and separately recovering the fraction containing the morpholine ethanol ethyl ether. 5. The process of converting a pp’ dihalogen 15 ated dialkyl ether to a morpholine alkanol ethyl ether, which comprises reacting a 13;?’ dihalogen mainder of the mixture, fractionally distilling the said layer, and separately recovering the fraction 20 containing the morpholine ethanol ethyl ether. 3. The process of making morpholine ethanol ethyl ether, which comprises hydrogenating mor pholine ethanol vinyl ether in the vapor phase caustic alkali, thereby producing a morpholine alkanol vinyl ether, hydrogenating the latter in in the presence of a hydrogenation catalyst, treat 25 ing the resultant reaction mixture near the boil tion catalyst, heating the resultant reaction mix ing temperature with aqueous acid solution, re acting the mixture with an excess of strong alkali, thereby effecting strati?cation of the mix ture into a plurality of layers including an amine 30 layer, separating the amine layer from the re mainder of the mixture, fractionally distilling the said layer, and recovering the fraction boiling around 204° to 206° C. under atmospheric pres ated dialkyl ether with an aqueous solution of a compound selected from the group consisting of ammonia and a morpholine, treating the re 20 sultant reaction mixture with an excess of a the vapor phase in the presence of a hydrogena ture with an aqueous solution of an inorganic 25 acid, treating the acidi?ed mixture with an excess of a strong alkali thereby stratifying the mixture into a plurality of layers including an amine layer, fractionally distilling the latter, and sepa 30 rately recovering therefrom the fraction contain ing the saturated morpholine alkanol ethyl ether. ALEXANDER L. WILSON.