Патент USA US3087007код для вставки
Q ‘ 3,086,997 ,7 Patented App. 23,’ i963 l ' ' g . w 3,086,997 l . . .' . ch arge d to the reactor _ Then H28 was added until the Paulsygvlgxseis gg?glggsimillgfgs‘gg?j‘?gg??ps ture was then heated to 150° F, and ethylene oxide hydroxide was all converted to hydrosul?de. This mix . , . , . .. Petroleum Company, a corporation of Delaware No Drawing. Filed N0“ 7, 1961’ Sen No_ 159,632 3 Claims, ((11, 260.409) (110g) was added over a period of 7 minutes. The 5 reactlon temperature rose to 125° F. and the pressure to 40 psig. After allowing a few ‘minutes .to complete the reaction, the reactor product was neutralized with This invention relates to a novel synthesis of 2-mersulfuric acid (80 ml., 98 percent) to a‘ pH of 3. Two captoethanol. In one of its aspects the invention relates phases were present; to the synthesis of 2amercaptoethanol by ?rst inter-react- 10 ‘ ' . . ‘ r Grams ‘ ing sodium hydroxide and hydrogen sul?de to form sodium hydrosul?de and then inter-reacting the reaction mass with ethylene oxide and then neutralizing the ?nal Organic phase _____________________________ __ 287 Water phase _______________________________ __ 446 reaction mass thus obtained. . . . . organic phase showed that it contained approximately . Zmercaptoethanol, which is valuable as a mercaptan - These were separated and an ASTM distillation on the . . l l ~ and am? as ‘a? wa alctohol? l‘argll Wélich (in ble 6r ‘Isou e 1' an p0 is prepara ‘on o 1 in £116 . ' ' Example II A stainless-steel autoclave with a l-qu-art capacity was 2H0CHzOHzSNa+HrSO4—>H0CHzOH2SH+Na2s04 used. Charge data on the run are as follows. Charge: By proceeding according to the foregoing reactions it is possible to obtain the 2~mercaptoethanol without the 25 formation of thiodiglycol. Thus in one process known to me 2-mercaptoethanol and oxidethiodiglycol and hydrogen are sul?de. obtainedThis by can reaction be illustrated of ethylene by the following reactions. 30 g ' M°1es 53g 110 Pressure,p_si2 / \ 156_225_ _ 25-45. 35 yrogflaatcggltlégmemm-l ------------------------------------ -- 7 H2804 (cohcentmted) added _____________________________ H 80‘ CH2———->HOCHlCH2SCH2CHzOH It is an object of this invention to provide a novel syn- p thesis for Z-mercaptoethanol. It is a ‘further object of _ 3. §3313553353581F_-;;;--;;;~-----------;;;;;;;;;;;;;;;; this invention to provide a method for producing Z-rner- captoethanol without the formation of thiodiglycol. 25 l om??gj‘mumy s F O HOCH2CH2SH+CH2 i ?aq?m OH2~CHZ~0 percent) .............................. ---------------------- " -- / \ 0H2 CH2+HiS—>HOOH2OHnSH (2) . 5400 F) 20 c§2_\_CH2+NaSH___,HOCH2OH2SNa (1) . above 250° F. The distillation end point was 328° F. showing that no thiodiglycol was formed (boiling point Les’ ‘ as been prepared, according to the present invention, by reactions which can be illustrated by the following: 50 percent Water and 50 percent of mater}a1 bmhng Distillation 0g No‘ 1 Organic phas 40 2%: ASTM 13-86, ‘’ 133M760 E‘B'IP' (2 9) Other aspects, objects and the several advantages of No‘zwater phase‘ this invention are apparent from a study of this dis closure .and the appended claims. According to the present invention there is provided a process for the synthesis of Z-mercaptoethanol which 45 comprises inter-reacting sodium hydrosul?de and ethylene loxide at an elevated temperature, and after completion of the reaction thus obtained, neutralizing the reaction mass and recovering Z-mercaptoethanol tralized mass thus obtained. from the __________ __ gilglgfzgg?gét-éaf-r-agx??. 1 of 1\l0_101‘ganic phase ______________ __ 144 g_ neu— Theoreticalyield ~ - - - - - - - - — - — In a now preferred form 50 of the invention sodium hydroxide and water are charged - - - — ~- 195 g 1 Required to add. the ethylene oxide. _ _ _ to a reactor. Then hydrogen sul?de is added to convert . It W111 be noted that m the ?ol'egmPg examples the‘re the sodium hydroxide to hydrosul?de. The mixture thus obtained is heated to approximately 150° F. Ethylene 1? a Pompleté absence of heif-vy‘end‘s 111 the d‘ls UH‘a-UQH- T1115 Shows that thlodl'glycol, the bolllng Polllt oxide is then added over a period of a few minutes. 55 of Whlch, as stated’ 15 540° F» was not formed The reaction temperature and pressure are allowed to rise and after a few minutes, for completion of the ,re_ When the alkali metal hydrosul?de and ethylene oxide are reacted the temperature is elevated. ‘One skilled in action, the reaction product is neutralized with sulfuric the’ art havlng Studled this dlsdo‘suIe W111 detelmlne a acid to a PH of 3, obtaining two phases, namely an Op ‘desirable temperature. However, the results which have game Phase and a water phase. 60 been obtained and which have been set out herein can On separating the phases and distilling the organic ‘be Obtamed by F‘ldmg'ethylene Oxide to the_sodlum hy phase a distillation end point of 328° F_ can be ob_ drosul?de-zcontalnlng mass at a temperature in the range tained showing that no thiodiglycol has been formed. of 125 to 250° F; _ Thiodiglycol boils at 540s R _ _ _ Reasonable variation and modi?cation are possible It will be evident to one skilled in the art reading this 65 “£11111 the S€°Pe °f 111? fmgomg ‘1186mm and the disclosure that other alkali metal hydroxides vcan be f‘lPPend6d clams m the mventlon ‘the essence,“ Whlch used and that neutralization can be effected with other 15 that_2‘mer°aPt°§than°1 has been Prepared Wlthout the acids_ formation of thlodlglycol by inter-reacting sodium hydro Example I sul?de and ethylene oxide and then converting the re A run was made in a 1-liter stainless-steel reactor. Sodium hydroxide (100 g.) and water (400 g.) were 70 action mass thus obtained by neutralizing the same with sulfuric acid, ultimately obtaining from the ?nal reaction mass the 2-mercaptoethanol. 3,086,997 3 4 \I claim: 1. A method of preparing Z-rne-rcaptoethanol which hydrogen sul?de into a_ reaction zone to produce therein sodium hydrosul?de, heating the sodium hydrosul?de thus produced to a temperature of approximately 150° F., then adding ethylene oxide and then neutralizing the comprises interreactinlg sodium hydrosul?de and ethylene oxide and then neutralizing the reaction mass thus obtained. _ 2. A process of preparing 2~mercaptoethano1 which 5 comprises interreacti'ng sodium hydrosul?de and‘ ethylene oxide at, a temperature in the range 1i25-250° F. and then sul?uri'c" neutralizing acid following the reaction which amass ?nal thus mass obtained thus obtained 10 is subjected to a recovery process ‘?or‘ recovering 2 me'rcaptoethanol. v ?nal reaction mass thus obtained with sulfuric acid and recovering 2¢mercaptoethanol fnorn the neutralized ?nal reaction mass. References Cited in the ?le of this patent FOREIGN PATENTS 769,216 France ______________ __ Aug. 22, 1934 _ 3'. A process‘ for the” preparation‘ of 2-1meroaptoethano1 which comprises charging sodium hydroxide, water‘ and OTHER REFERENCES Sjoberg- Ber. Deu-t. Chem. 74, 64-72 (1941).