Патент USA US2408302код для вставки
Patented Sept. 24, 1946 2,408,300 :~: T OFFICE?! .nYnRoLYsIs 0F ALIPHATIC‘ SULPHONYL . CHLORIDES . .. . ‘Thomas Edward Dillon, New Castle, Del.,- assignor - " to E; I. du'Pont de, Nemours & Company, Wil-l mington, DeL, a corporation of Delaware ‘ -. seeming. ‘Application October 30, 1945, ' _ ‘Serial ‘No. 625,085 ' ’ > " 5 claims. ' (01. 260-513)’ - s. a I ; 1 . . 11, . said limiting quantity would normally beem‘:~ .This'iin'vention' relates tola method tor hy drolyzing organic'sulphonyl chlorides. More-par ployed. ~ ' - . . I have found that the use of such auxiliary ~ quantities of an active organic nitrogenous base . ticularly, this invention"deals with a process for preparing- aliphatic sulphona'tes by alkaline hy-. drolysis of aliphatic sulp'honyl chlorides. - has the e?ect of lowering the hydrolysis tem perature, shortening the timeof hydrolysis, pre-. venting excessive foaming and decreasing-the ' .The mentioned aliphatic sulphonyl ‘chlorides ’ are generally prepared by reacting‘ with a gase ous mixturev of sulphur dioxide and chlorine or; alternatively. with sulphuryl ‘chloride and a'cata lyst, in the presence: of actinic light, upon'satu rated aliphatic hydrocarbons having various viscosity of the reaction mass.“ All of theserij‘acy tors, together have the further; effect of: increas ing the active-ingredient contentotthe' product; 10 inasmuch ,as_'decomposition or desulphonationlof the product _during;the hydrolysis step is held by: chain lengths (from "4' ‘to '50'carbon atoms) and ' the above factors at a minimum. The saiddecom-U ' position of the ,sulphonyllchloride appears to be these’p'roc’esses,’ among‘ which the following‘ may 15 a vfunction of the,;.temperature, and accordingv being straightich'ained or branched. . Numerous‘ patents ,have issued describing‘ and claiming‘ tov my invention, hydrolysis proceeds su?icient 1y rapidly at lower temperatures so that. excessive; decomposition is avoided. be. mentioned 'as ‘typical: Reed, Re. $20,968; Reed, 2,174,492; Fox etal,‘ 2,174,506‘; Tinker et 2.1., 2,174,507; Fox ‘et al., 2,174,508; Lockwood et;al., 2,193,824; Henke et al., 2334364; and Kharasch, I 20 ~~The products‘fof'theabbveflreaction are gen-‘ _ . ' _ ~ I . In practice according to my ‘invention, the sul-_E ' 2,383,319. ' ‘ phonylated reaction mass may be fed gradually into a mixtureV of the aqueous alkali and the seV erally .mono-,' di- or "polyesulph'onyl' chlorides, lected-nitrogenous base. Alternatively, a mixture - generally ‘been-achieved by reacting upon said sulphonyl chlorides'with' aqueous alkali, particu and then add the aqueousalkali. . of "the nitrogenous-base and the aqueous alkali oftenihaving one or more chlorine atoms attached mayvbe ‘fed slowly into the sulphonylation mass. directly to carbon atoms in the molecule. ~ The hydrolysis of ‘the aforegoin'g compounds to 25 A third option is to enter ?rst the selected nitrog enous baseinto the sulphonylated reaction mass. the gcorresponding ' sulphonates ‘has hitherto 1 . The temperature of the mass during the hy-: larly aqueous caustic 'soda. . Typical procedures drolysis step may‘ vary. from'room temperature. forT-jthis. purpose have beenv described'in the above mentioned U. S. Jpatents‘ ‘as well as in‘ Reed. torl20PpC. or higher. But inasmuch as it is de-' 2,174,110 and‘Reed,v 2,276,090. 7 - sirable to keep decomposition down .to a mini mum,‘ it ispreferred in practice to effect hy-' ‘ drolysis at as low a temperature asis consistent with good speed, say within a range of 70° to "'In‘TJ'. S. Patent" No.‘ 2,319,121, arproposallhas' employ alcohols as? hydrolyzing’g been ': made ' to agents.‘ ' ' 105°C.‘ " , a " " ' , 1 - The present invention"isFconcerned primarily "Without limiting my invention, the following with ‘the caustic alkali method vof hydrolysisPand' ' examples are given to illustrate my preferred mode of operation. it; is 'an‘object of this invention to improve said weight method in a'general way,=wh'ereby_to facilitate hydrolysis and to produce better quality products; Other and further important‘objects of "this in vent'ion will appear as ‘the ‘description proceeds." "I' have found that several- ‘distinct improve-._ ments,_as_more_fully discussedbelow, are obtained if the hydrolysis of ' thelabove indicated. organic sulphonyl chlorides is‘ e?ected by the aid’ of aqueous alkali inthe'presence of a small quan-. tity ofzan aCtivebrganic nitrogenous base. ' By “active? I means that‘ the'base will readily form, a’, saltwith hydrogen chloride. By “small quan 40 - Parts mentioned are "byv ., v I Example 1 'A mixture of 336 parts of S02 and 267 parts of chlorine was passed into 300 parts of molten re?ned para?in .wax (M. R. ‘120-122? F., ‘A.’ S'; V ‘T. M.) while the mass was agitated and exposed .‘ to actinic light as described in U.IS. Re. 20,968. The product was then hydrolyzed by adding gradually with agitation to a mixture of 262 parts of 50% aqueous sodium hydroxide solution and 7.5 parts of Solvent P (the commercially‘ avail 50 able mixture . of I mono-, 'di-,' and vtri-ethanol tity"~l_meanany quantity less than that which ._ I amines) ,‘ maintained at a temperature between 85 would byitseli su?lcetoefiect‘hydrolysis oi the ‘and 90° C. V The hydrolysis mass was noticeably‘ museum vor . sulphonyl ;.ch.1Qiide. although thinner and-smoother throughout than in a‘ simi in. the; were. .ordinarrrracticeless than. 20% ‘or; 55 . lav-hydrolysis in. absence of any amine. The _re_.. 2,408,300 3 4 action was also completed in a much shorter the product used had 190-210" C. time, without foaming dii?culty, and the product a boiling range of The product was hydrolyzed by-adding grad was obtained in better yield and quality. Example 2 A ‘mixture ‘ofv 116 parts of S02 and. 83 parts of C12 was passed into 324 parts of No. .40 white oil ually to 294 parts of 40% aqueous NaOH con taining 9.6 parts of pyridine while maintaining the temperature in the range~95-105° C. The hydrolysis mass was diluted with alcohol'and ?l in a manner similar to that described in Exam tered, unreacted oil was separated and the con-' ple 1. This oil is a saturated petroleum fraction ‘centration of the remaining mass was adjusted of boiling range 265-300° 0., sp. gr. 0.801 and 10 to 50% of active ingredient. The mass remained Saybolt Universal Viscosity 36-37 sec. at 100° F. thin and smooth during the hydrolysis, with no The resulting product was hydrolyzed by add foaming and a good yield of light colored prod ing gradually to 242 parts of an aqueous 730% , uct'was obtained. Similar results were obtained sodium hydroxide solution containing 4 parts of _ morpholine, while maintaining the temperature , at 75-85° C. The hydrolysis mass was further diluted with water until the unreactedv oil;sepa-.: rated. The latter was removed and the hydro lyzed product, after addition of sodium sulphate by .using'..9.6 parts of trimethylamine in place of .the pyridine. ‘ It will be understood that the details in the above examples may be varied within wide lim-‘ its, without departing from the spiritof this invention. Thus, the alkaline solution may be and borax, was evaporated to dryness on a drum 20 heated to 70°-80° C. prior to neutralization or dryer. Advantages similar to those described in may be at room temperature before beginning Example 1 were found in having the amine the addition of sulphonyl chloride. present. , In place of the nitrogenous‘base's named in 7 Example 3 the examples, many others may be used, tonin A- mixture of 95'parts of 902V and 76 parts of 25 stance, pyridine, -piperidine,-pic'oline', nion‘o-gr'die, or tri-ethanolamine, morpholine, N-methylrmor 612- was passed into 270 parts of No.30 whitev oil pholine, or diethyl-cyclohexyl amine. ‘In- general, as previously described. This- oil is a‘ completely it is believed that any nitrogen base which read saturatedpetroleum fraction typically with a ily forms a hydrochloride salt will assist inthe boiling range of 210-2509 0., sp. gr. 0.781 and neutralization of the aliphatic 'sulphoriyl "chlol Saybolt-Universal Viscosity oi? 32-33 sec. at 100° F. The sulphonylated product-was hydrolyzed as rides. ous NaOH-containing 2 parts o'f'monoethanola mine, while.‘ maintaining‘ the temperature at 80-85°'C. The mass‘was dilutedsoias to'contain ' about’ 22% of active ingredient, the. oil was sep arated and‘the aqueous'product was used in this form. The hydrolysis proceeded smoothly in the presence-of the monoethanolaminea _} Example 4 . For some uses the small amounts 'of amine previously d'escribedwith-1365 parts of 20% aque u left in the product may be objectionable if an amine with an unpleasant odorsuch as the methyl amines, pyridine, etc., is'used as thechydro'lysis catalyst. For such uses it is‘usually, ‘preferable to employ odorless ‘amines such as ,therethanol. amines. On the other hand, the unpleasant smelling amines may be removed or chemically altered after the hydrolysis, in knownmanner' such as by treatment with ethylene oxide, oxida A mixture of-106 parts of re?ned; para?iin' wax and 19 parts of petrolatum was treated‘ with. 88 tion; etc. Similarly, aromatic amines may'ibe objectionable where the product is to be‘ us'ediin parts of S02 and 49 parts of C12 :aspreviously personal contact. described.‘ The hydrolysis was carried out with: 1125 parts‘ of 50% aqueous NaOH. in the presence of..5:. parts . for complete neutralization‘ of th’e'sulphonchlo; ride. ‘However, 1-3%,on- the weight or the stile phonylation mass" has‘ been found to produce‘ the: of pip-eridine. The hydrolysis was startedat room temperature and the temperature was allowed to. rise to 70° C. during hydrolysis. 'Thehydrolye sis' proceeded smoothly without formation or lumps and the product was alight cream coloredv paste ready for use. Example 5 , The concentration of the amine used in cata lyzing the hydrolysis may vary from 1% up to‘ 15% or 20% of the theoretical quantity required: ' most‘ desired effect at minimum cost. .. >, A mixture of 285 parts‘ of re?ned paraffin: wax and 0.97 parts‘ of stearamide was ‘heated to$70° C. and 428 parts of sulphuryl chloride was added over a period of 4 hours while irradiating with actinic light as described in U. S. 2,383,319. To this mixture was added 15; parts of tri by the above examples. ethanolamine, then 192 parts of‘ 65% aqueous when di-, and polysulphonates are being hy _ The effects produced when-using the'auxiliary' amines during hydrolysis are morenoticeable NaOH was gradually‘ added with agitation "while maintaining the temperature. in‘. the: range 85-95" , C. ‘The hydrolysis" proceeded smoothly‘ and- rapid’ 1y, yielding a smooth cream colored’ paste. ' Example. 6 A mixture‘ of 187: parts of SO‘zi'an‘d‘ 145 parts of Cll.r was passed into320 parts'of “alkyllatio'n' bot toms” with. agitation and irradiation. “alkylation bottoms” ‘consists ot a mixtureloti' saturated branched chain hydrocarbons-obtained as". a: byproduct . from‘ isosocta‘ne' mama-aw ' As for the alkali, potassium hydroxide, calcl-iim hydroxide, or other metallic hydroxidesiwhich react with sulphonyl chlorides maybe used for neutralization actual vpractice,in however, lieu of sodium sodiumhydroxide. :hydroxidei'is prob-ably the only one that would-normally‘ be‘ used. ,The concentration of the "alkali may vary" appreciably, say from. 20% to 65%, as illustrated. drolyzed. 6E’ , f ‘ " In general, all aliphatic hydrocarbon s‘lil'pl'ionyl chlorides may be neutralized iii this'irianr‘iei'. The advantages ofr‘my invention may‘ ‘now be summarized- as follows‘; The aminfe catalyst keeps the hydrolysis mass‘ thin‘, throughout and pre; vents‘ formation and development‘ of local acidity. Such local acidity causes‘ desulphonylation' results in troublesome foaming; of the hydrolysis mass asv well as-Ios'sin yield. ; With a'g-ivlenl degree‘ of; agitation ‘ and a given temperature "thétfmeof hydrolysis is- considerably shortened, reducing- the" 2,408,300 5 . Y cost of the product by increasing the capacity ' 'ing upon said sulphonyl chloride with an aque of the equipment; alternatively, the same reaction time may be achieved at a lower temperature. ous solution of a‘caustic alkali in quantity sub The disadvantage vof increasing temperature to reduce the reaction time, rather than using the catalyst, is that desulphonylation increases with increasing temperature and this reduces yield and quality of product. Also,- although the hydrolysis is improved by improving the agitation such im provement is often limited by the tendency to foam. When proceeding according to my inven tion, the tendency to foam is considerably re stantially equalto that theoretically required for complete hydrolysis and in the presence of less than the stoichiometric quantity of an ‘organic nitrogenous base .7 which is sufficiently basic to g ' form a salt with hydrogen chloride. 4. A process of hydrolyzing an aliphatic sul- ' phonyl chloride to produce a salt of the corre sponding sulphonic acid, which comprises react ing upon said sulphonyl chloride with aqueous caustic alkali in quantity substantially su?icient to e?ect by itself the desired hydrolysis, said duced. ‘ » aqueous alkali containing further a quantity of I claim as my invention: I 1. In the process of hydrolyzing an aliphatic 15 an organic nitrogenous base corresponding in molar proportion to not over 20% of the quantit sulphonyl chloride by reacting "upon the same of the caustic alkali employed. " with aqueous caustic alkali, the improvement 5. The process of hydrolyzing an aliphatic sul which consists in effecting the reaction in the, phonyl chloride to produce the corresponding so presence of an organic nitrogenous base. 2. A process of hydrolyzing an aliphatic sul 20 dium sulphonate, which comprises entering said organic sulphonyl chloride, at a temperature of phonyl chloride to produce a salt of the corre about 80° to _100° 0., into an aqueous solution of syponding sulphonic acid, which comprises re sodium hydroxide of 30% to 50% strength and acting upon said sulphonyl chloride with a mix containing a quantity of an organic nitrogenous ture of a caustic alkali and an organic nitrog base corresponding to from 1% to 3% by weight enous base in an aqueous medium.' 25 of the organic sulphonyl chloride to be treated. 3. A process of hydrolyzing an aliphatic sul phonyl chloride to produce a salt of the’ corre ' spending sulphonic acid, which comprises react-' THOMAS EDWARD DILLON.