DE942027C - Process for the preparation of substituted 2-iminothiazolidines - Google Patents
Process for the preparation of substituted 2-iminothiazolidinesInfo
- Publication number
- DE942027C DE942027C DEA20924A DEA0020924A DE942027C DE 942027 C DE942027 C DE 942027C DE A20924 A DEA20924 A DE A20924A DE A0020924 A DEA0020924 A DE A0020924A DE 942027 C DE942027 C DE 942027C
- Authority
- DE
- Germany
- Prior art keywords
- substituted
- iminothiazolidines
- preparation
- salts
- thiourea
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 8
- REGFWZVTTFGQOJ-UHFFFAOYSA-N 4,5-dihydro-1,3-thiazol-2-amine Chemical class NC1=NCCS1 REGFWZVTTFGQOJ-UHFFFAOYSA-N 0.000 title claims description 6
- 238000002360 preparation method Methods 0.000 title claims description 3
- 150000003839 salts Chemical class 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001414 amino alcohols Chemical class 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- KWGRBVOPPLSCSI-WPRPVWTQSA-N (-)-ephedrine Chemical compound CN[C@@H](C)[C@H](O)C1=CC=CC=C1 KWGRBVOPPLSCSI-WPRPVWTQSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229960002179 ephedrine Drugs 0.000 description 2
- NJYFRQQXXXRJHK-UHFFFAOYSA-N (4-aminophenyl) thiocyanate Chemical class NC1=CC=C(SC#N)C=C1 NJYFRQQXXXRJHK-UHFFFAOYSA-N 0.000 description 1
- GMFUTRCIEWHKBH-UHFFFAOYSA-N 3,4-dimethyl-5-phenyl-1,3-thiazolidin-2-imine Chemical compound S1C(=N)N(C)C(C)C1C1=CC=CC=C1 GMFUTRCIEWHKBH-UHFFFAOYSA-N 0.000 description 1
- WNDFVBQJYJRMQO-UHFFFAOYSA-N 3,4-dimethyl-5-phenyl-1,3-thiazolidin-2-imine;thiocyanic acid Chemical compound SC#N.S1C(=N)N(C)C(C)C1C1=CC=CC=C1 WNDFVBQJYJRMQO-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- KWGRBVOPPLSCSI-UHFFFAOYSA-N d-ephedrine Natural products CNC(C)C(O)C1=CC=CC=C1 KWGRBVOPPLSCSI-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D277/18—Nitrogen atoms
Description
Verfahren zur Herstellung von substituierten 2-Iminothiazolidinen Es wurde gefunden, daß substituierte 2-Iminothiazolidine der allgemeinen Formel , worin R einen aromatischen und R1 und R2 aliphatische Reste bedeuten, in vorteilhafter Weise dadurch erhalten werden, daß man entsprechend substituierte Aminoalkohole der allgemeinen Formel worin R, R, und R2 die obige Bedeutung haben, oder deren Salze mit Thioharnstoff bei Temperaturen von z8o bis 25o° zusammenschmilzt, wobei die substituierten Iminothiazolidine als Hydrorhodanide erhalten werden, aus denen nach bekannten Methoden beliebige Salze mit anderen Säuren hergestellt werden können. Es sind zwar schon Verfahren bekanntgeworden, nach welchen man das 2-Imino-3, 4-dimethyl-5-phenyl-thiazolidin durch Umsetzung von Chlorephedrinhydrochlorid mit Rhodansalzen erhält, wobei gegebenenfalls I-Phenyl I-rhodan-2-methylaminopropan als Zwischenprodukt entsteht (vgl. z. B. die deutsche Patentschrift 841 I49). Vor diesem bekannten Verfahren hat das erfindungsgemäße Verfahren den wesentlichen Vorteil, daß es nicht erforderlich ist, z. B. aus Ephedrin zuerst das I-Phenyl-I-halogen-2-methylaminopropan und aus letzterem in einer oder. zwei weiteren Reaktionsstufen das entsprechende 2-Iminothiazolidin herzustellen. Da die r-Phenyli-halogen-alkylaminopropane wegen ihrer leichten Zersetzlichkeit in Form ihrer beständigeren Salze mit Mineralsäuren angewandt werden müssen, muß in dem Reaktionssystem mit Rhodansalz gleichzeitig der die Cyclisierung erschwerende Säurerest mit in Kauf genommen werden. Diese Nachteile werden bei dem in einer einzigen Reaktionsstufe verlaufenden neuen Verfahren vermieden, bei dem der Säurerest des als Ausgangsverbindung verwendeten Salzes des Aminoalkohols durch das im Verlauf der Reaktion sich abspaltende Ammoniak gebunden wird.Process for the preparation of substituted 2-iminothiazolidines It has been found that substituted 2-iminothiazolidines of the general formula in which R is an aromatic radical and R1 and R2 are aliphatic radicals, are advantageously obtained by using correspondingly substituted amino alcohols of the general formula where R, R, and R2 have the above meaning, or their salts melt together with thiourea at temperatures from 80 to 25o °, the substituted iminothiazolidines being obtained as hydrorhodanides, from which any salts with other acids can be prepared by known methods. Processes have already become known according to which 2-imino-3, 4-dimethyl-5-phenyl-thiazolidine is obtained by reacting chlorephedrine hydrochloride with rhodane salts, with I-phenyl-I-rhodane-2-methylaminopropane as an intermediate product ( see e.g. the German patent specification 841 I49). Before this known method, the inventive method has the significant advantage that it is not necessary, for. B. from ephedrine first the I-phenyl-I-halogen-2-methylaminopropane and from the latter in one or. two further reaction stages to produce the corresponding 2-iminothiazolidine. Since the r-phenyli-halo-alkylaminopropanes have to be used in the form of their more stable salts with mineral acids because of their ease of decomposition, the acid residue which makes the cyclization more difficult must also be accepted in the reaction system with rhodan salt. These disadvantages are avoided in the new process, which proceeds in a single reaction stage, in which the acid residue of the salt of the amino alcohol used as the starting compound is bound by the ammonia which is split off in the course of the reaction.
Beispiel =o,= g dl-Ephedrinchlorhydrat werden mit 12,9 g Thioharnstoff auf Zoo bis 21o° für die Dauer von z1/2 Stunden erwg=.mt, wobei unter Gasentwicklung 2-Imino-3, 4-dimethyl-5-phenylthiazolidinhydrorhodanid gebildet wird. Nach dem Erkalten wird das Reaktionsgemisch unter kräftigem Umrühren mit Wasser versetzt, wobei allmähliche Kristallisation eintritt. F. = 192°. Ausbeute 9,5 g = 710/, der Theorie.Example = 0, = g of dl-ephedrine chlorohydrate are heated with 12.9 g of thiourea at a temperature of up to 210 ° for a period of 1/2 hours, with 2-imino-3, 4-dimethyl-5-phenylthiazolidine hydrorhodanide being evolved is formed. After cooling, the reaction mixture is admixed with water while stirring vigorously, with gradual crystallization occurring. F. = 192 °. Yield 9.5 g = 710 /, of theory.
Claims (1)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEA20924A DE942027C (en) | 1954-08-11 | 1954-08-11 | Process for the preparation of substituted 2-iminothiazolidines |
| DEA21014A DE944551C (en) | 1954-08-11 | 1954-08-26 | Process for the preparation of substituted 2-iminothiazolidines |
| BE539997A BE539997A (en) | 1954-08-11 | 1955-07-22 | PROCESS FOR THE PREPARATION OF 2-IMINOTHIAZOLIDINES SUBSTITUTES. |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEA20924A DE942027C (en) | 1954-08-11 | 1954-08-11 | Process for the preparation of substituted 2-iminothiazolidines |
| DEA21014A DE944551C (en) | 1954-08-11 | 1954-08-26 | Process for the preparation of substituted 2-iminothiazolidines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE942027C true DE942027C (en) | 1956-04-26 |
Family
ID=32870156
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEA20924A Expired DE942027C (en) | 1954-08-11 | 1954-08-11 | Process for the preparation of substituted 2-iminothiazolidines |
| DEA21014A Expired DE944551C (en) | 1954-08-11 | 1954-08-26 | Process for the preparation of substituted 2-iminothiazolidines |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEA21014A Expired DE944551C (en) | 1954-08-11 | 1954-08-26 | Process for the preparation of substituted 2-iminothiazolidines |
Country Status (2)
| Country | Link |
|---|---|
| BE (1) | BE539997A (en) |
| DE (2) | DE942027C (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH266997A (en) * | 1948-06-04 | 1950-02-28 | Ballmer Paul | Process for the preparation of 3,4-dimethyl-5-phenyl-2-imino-thiazolidine. |
| DE841149C (en) * | 1949-11-01 | 1952-06-13 | Knoll Ag | Process for the preparation of 3, 4-dimethyl-5-phenyl-2-iminothiazolidine |
| CH284072A (en) * | 1950-02-09 | 1952-07-15 | Ballmer Rueedi Paul | Process for the preparation of 3,4-dimethyl-5-phenyl-2-imino-thiazolidine. |
-
1954
- 1954-08-11 DE DEA20924A patent/DE942027C/en not_active Expired
- 1954-08-26 DE DEA21014A patent/DE944551C/en not_active Expired
-
1955
- 1955-07-22 BE BE539997A patent/BE539997A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH266997A (en) * | 1948-06-04 | 1950-02-28 | Ballmer Paul | Process for the preparation of 3,4-dimethyl-5-phenyl-2-imino-thiazolidine. |
| DE841149C (en) * | 1949-11-01 | 1952-06-13 | Knoll Ag | Process for the preparation of 3, 4-dimethyl-5-phenyl-2-iminothiazolidine |
| CH284072A (en) * | 1950-02-09 | 1952-07-15 | Ballmer Rueedi Paul | Process for the preparation of 3,4-dimethyl-5-phenyl-2-imino-thiazolidine. |
Also Published As
| Publication number | Publication date |
|---|---|
| DE944551C (en) | 1956-06-21 |
| BE539997A (en) | 1959-07-17 |
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