PL814B1 - The method of obtaining methyl-sulphite salts of low-grade aromatic-aliphatic amines. - Google Patents
The method of obtaining methyl-sulphite salts of low-grade aromatic-aliphatic amines. Download PDFInfo
- Publication number
- PL814B1 PL814B1 PL814A PL81421A PL814B1 PL 814 B1 PL814 B1 PL 814B1 PL 814 A PL814 A PL 814A PL 81421 A PL81421 A PL 81421A PL 814 B1 PL814 B1 PL 814B1
- Authority
- PL
- Poland
- Prior art keywords
- aliphatic amines
- aromatic
- methyl
- condensation
- parts
- Prior art date
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- QFUDHWDUKUCCHZ-UHFFFAOYSA-N methyl hydrogen sulfite Chemical class COS(O)=O QFUDHWDUKUCCHZ-UHFFFAOYSA-N 0.000 title claims description 5
- 238000000034 method Methods 0.000 title claims description 4
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- DETXZQGDWUJKMO-UHFFFAOYSA-N 2-hydroxymethanesulfonic acid Chemical compound OCS(O)(=O)=O DETXZQGDWUJKMO-UHFFFAOYSA-N 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- IUQXMAXWSJDJAY-UHFFFAOYSA-N S(=O)(O)OS(=O)O.C=O Chemical compound S(=O)(O)OS(=O)O.C=O IUQXMAXWSJDJAY-UHFFFAOYSA-N 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- 150000003142 primary aromatic amines Chemical class 0.000 claims description 2
- 150000003839 salts Chemical group 0.000 claims description 2
- OJGMBLNIHDZDGS-UHFFFAOYSA-N N-Ethylaniline Chemical compound CCNC1=CC=CC=C1 OJGMBLNIHDZDGS-UHFFFAOYSA-N 0.000 claims 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- -1 aldehyde bisulfite Chemical class 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- NVJBFARDFTXOTO-UHFFFAOYSA-N diethyl sulfite Chemical compound CCOS(=O)OCC NVJBFARDFTXOTO-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- GYYQGTREJKJFLN-UHFFFAOYSA-N S(=O)(O)O.C[Na] Chemical compound S(=O)(O)O.C[Na] GYYQGTREJKJFLN-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001754 anti-pyretic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 235000021028 berry Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000004682 monohydrates Chemical class 0.000 description 1
- GTWJETSWSUWSEJ-UHFFFAOYSA-N n-benzylaniline Chemical class C=1C=CC=CC=1CNC1=CC=CC=C1 GTWJETSWSUWSEJ-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HRZFUMHJMZEROT-UHFFFAOYSA-L sodium disulfite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])(=O)=O HRZFUMHJMZEROT-UHFFFAOYSA-L 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 235000010262 sodium metabisulphite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
Description
Wykryto, ze produkty, otrzymywane przez kondensacje amin aromatyczno-alifa¬ tycznyeh drugorzedowych z dwusiairczynem aldehydonirówkowym, albo tez produkty, otrzymane przez alkilowianie pochodzacych z kondensacji amin aromatycznych pierw- szorzedowych z dwusiarczynem aldehydo- mrówkowym, w stosunku do otrzymanych soli metylosiarczynowyeh róznia sie od tam¬ tych amin aromatycznych pieirwszorzedo- wych znacznie silniejsizem dzialaniem anti- pyretycznem, Produkty kondensacji tworza stale pola¬ czenia, w wodzie latwo rozpuiszczialne, któ¬ re sie pod dzialaniem kwasów rozkladaja.Z patentów niemieckich 153196 i 156760 wiadomo, ze niektóre aminy aromatyczno- alifatyczne podlegaja kondensacji z dwu¬ siarczynem aldehydomrówkowym. Wyszcze¬ gólnione w tych patentach i nalezace tutaj polaczenia metylo- etylo- i benzylo-aniliny nie poisiadaja jednak wyraznych wlasciwo¬ sci terapeutycznych.Nastepujace przyklady wyjasniaja meto¬ de niniejsza: 1. N-metylo- p-femety¦dyino'- metylosiiar- czyn sodu: 8,2 czesci 36, 6°/0-wego roztworu alde¬ hydu mrówkowego, 26 czesci 40°/0-w:ego roztworu dwusiarczynu sodu, 15 czesci me- tylofenetydyny i 25 czesci alkoholu nagrze¬ wa sie az do wrzenia. Pow&taje roztwór jed^ nonodny i nastepuje wydzielenie produktu reakcji. Nalezy odessac i oczyscic przy po¬ mocy rozwodnionego alkoholu. Substancja ta rozklada sie w 265°, rozpuszcza latwow, wodzie i rózni sie od polaczenia, wymie- imidnego w patencie niemieckim 209695 teim, ze ziai dodaniem kwaisu solnego do roztwo- ni wodnego kwas organiczny sie nie wy¬ dzielaj,, zials zia doidamietm 'aizioftyjiuu nastepuje zabarwienie koloru krwistego i wydzielenie oleju. 2. N-etylo-p-feneityidynio metylo-siarczyn sodu: 40°/0 i 49 czesci etylofenetydyny miesza sie w ciagu kilku godzin w temperaturze 25—30° az do ujednostajnienia roztwoiru.Mniejisza czesc produktu reakcji krystalizuje juz przez noc, reszte zas mozna otrzymac po odparowaniu pozostalego iozczynu. Otrzy¬ mana sól, oczyszczona z alkoholu, nie wy¬ kazuje okreslonego punktu rozkladania sie.Wlasnosci tego nowego polaczenia sa te sa¬ me, co i polaczenia metylowego w przykla¬ dzie 1. 3. 1-fenylo- 2,3-dimetylo- 5-pynaizolonOh 4-etylo-amino-, metylo'Siarczyn sodu: Do 25 czesci etyloaiminoiantipyriny dole¬ wa sie 8,2 czesci jeszcze goracego roztworu reakcyjnego aldehydu mrówkowego 36,6°/a- wego i 26 czesci 40°/o-wego roizitworu dwu- siarczynu sodu, mieszajac wzystkoi, pocizeni ^wkrótce powstaje przejr&ysty roztwór. Roz¬ twór w celu odwodnienia odparowuje sie, najlepiej w prózni, i pozostalosc 0'Czyszezia sie rozwodnionym acetonem. Substancja to^ pi sie w swej wlasnej1 wodzie krystalicznej w temperaturze 80—90° i jest nadzwyczaj latwo rozpuszczalna wl wodzie,. Podczas rua^ grzewania z rozcienczonym kwasem solnym oddziela sie kwas siarkowy. 4. 1-fenylo- 2,3-dimetylo-' 5-pyirazolono- 4-etyloamiilno^ metylosiiiaircizyin sodu: Slabo nagrzany roizitwór z 32 czesci 1-feny¬ lo- 2,3-dimetylo-5-pyrazolonoi- 4-aminoimetylo siarczyn sodu i 6 czesci weglanu sodu w 150 czesciach wody wstrzasamy n 17 czesciami dwuetylosiarczynu. Po ukonczeniu reakcji nalezy odparowac az do krystalizacji i roz¬ puscic w ro:^cienoziony|m aicetontó., Otayima- na substancja topi sie miedzy 80 a 90° i jest identyczna z uzyskana w przykladzie! 3-cim. 5. N-etyloifenetydynoKmetyloisiarcizyn so¬ du: 50 czesci p-feinetydyno-metyloisiarezynu sodowego (zw. w handlu neralteineni) i 13 czesci weglanu sodu nalezy zagniesc z 34 czesciami dietyloi-siarczynu i podgrzewac na kapieli wodnej az do ukonczenia wydziela¬ nia sie Ca2 (72 godlziny). Mase reakcyjina mozna nastepnie oiczyscic z rozcienczoinego alkoiholu. Uzyskana ta droga substancja nie- posiada dokladnie okreslonego^ punktu roz¬ kladu i jest identyczna iz substancja, otrzy¬ mana w" przykladzie 2. « PL PLIt was found that products obtained by condensation of secondary aromatic-aliphatic amines with aldehyde bisulfite, or products obtained by alkylation from the condensation of primary aromatic amines with formaldehyde disulfite, in relation to the obtained methyl sulfite salts These first-order aromatic amines are much stronger than their anti-pyretic action. Condensation products form constant connections in water, easily dissolving in water, which decompose under the action of acids. From German patents 153196 and 156760 it is known that some aromatic-aliphatic amines are subject to condensation with formaldehyde bisulfite. The combinations of methyl ethyl and benzyl anilines specified in these patents and associated therewith do not, however, have remarkable therapeutic properties. The following examples explain the present method: 1. N-methyl-β-femety¦dyino'-methylsiiar- sodium act: 8.2 parts of a 36.6% solution of formic aldehyde, 26 parts of a 40% solution of sodium bisulfite, 15 parts of methylphenethidine and 25 parts of alcohol are heated until boiling. A monohydrate solution returns and the reaction product is isolated. Suction and clean with diluted alcohol. This substance decomposes at 265 °, dissolves easily, in water and differs from the combination mentioned in the German patent 209695 teim that the berry and the addition of hydrochloric acid to the aqueous solution of the organic acid do not separate "glands into the memory" aizioftyjiuu blood-colored and oil separation. 2. N-ethyl-p-pheityidinium methyl-sodium sulphite: 40 ° / 0 and 49 parts of ethylphenethidine are stirred for several hours at 25-30 ° until the solution becomes homogeneous. A smaller part of the reaction product crystallizes overnight, the rest can be obtained after evaporation of the residual iodine. The obtained salt, purified from alcohol, does not show any specific decomposition point. The properties of this new combination are the same as those of the methyl link in Example 1. 3. 1-phenyl-2,3-dimethyl- 5-pynaizolone, 4-ethyl-amino-, methyl'Sodium sulphite: 8.2 parts of the still hot 36.6% formaldehyde reaction solution and 26 parts of 40% of formaldehyde are poured into 25 parts of ethylaminoiantipyrine. Sodium disulfite solution, stirring the mixture, soon produces a clear solution. The solution for dehydration is evaporated, preferably in a vacuum, and the residue is cleaned with diluted acetone. This substance is drinkable in its own crystal water at a temperature of 80-90 ° and is extremely easily soluble in water. The sulfuric acid is separated off by heating with dilute hydrochloric acid. 4.Sodium 1-phenyl-2,3-dimethyl-5-pyrazolone-4-ethylamiline-methyl silicaircizyin: Slightly heated 32 parts 1-phenyl-2,3-dimethyl-5-pyrazolone-4-aminoimethylsulfite Shake 6 parts of sodium carbonate and 6 parts of sodium carbonate in 150 parts of water with 17 parts of diethyl sulfite. After the reaction is complete, it is necessary to evaporate until crystallization and dissolve in the formula: thinly thinned aicetont. The otayima substance melts between 80 and 90 ° and is identical to that obtained in the example! 3rd 5. Sodium N-ethylphenethidine Kmethyl sulphite: 50 parts of sodium p-phenethidine-methylisiaresin (commercially known as neralteinene) and 13 parts of sodium carbonate must be kneaded with 34 parts of diethyl sulphite and heated in a water bath until the release of Ca2 is complete (72 hours). The reaction mass can then be treated with diluted alcohol. The resulting expensive substance does not have a precisely defined decomposition point and is identical to the substance obtained in "Example 2."
Claims (2)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| PL814B1 true PL814B1 (en) | 1924-11-29 |
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