DE1241831B - Process for the preparation of crystalline 1, 6-bis-AEthylenimino-1, 6-dideoxy-3, 4-isopropylidene-D-mannitol - Google Patents
Process for the preparation of crystalline 1, 6-bis-AEthylenimino-1, 6-dideoxy-3, 4-isopropylidene-D-mannitolInfo
- Publication number
- DE1241831B DE1241831B DEG27455A DEG0027455A DE1241831B DE 1241831 B DE1241831 B DE 1241831B DE G27455 A DEG27455 A DE G27455A DE G0027455 A DEG0027455 A DE G0027455A DE 1241831 B DE1241831 B DE 1241831B
- Authority
- DE
- Germany
- Prior art keywords
- isopropylidene
- mannitol
- dideoxy
- bis
- crystalline
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title description 4
- NOWKCMXCCJGMRR-UHFFFAOYSA-N Aziridine Chemical compound C1CN1 NOWKCMXCCJGMRR-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000004821 distillation Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000594 mannitol Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000010533 azeotropic distillation Methods 0.000 description 1
- -1 benzene Hydrocarbons Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 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
- 230000020169 heat generation Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D203/00—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom
- C07D203/04—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings
- C07D203/06—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D203/08—Heterocyclic compounds containing three-membered rings with one nitrogen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring nitrogen atom
- C07D203/12—Radicals substituted by nitrogen atoms not forming part of a nitro radical
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Saccharide Compounds (AREA)
Description
Verfahren zur Herstellung von kristallinem 1 ,6-bis-Athylenimino-1,6-didesoxy-3 ,4-isopropyliden-D -mannit Die Erfindung betrifft ein Verfahren zur Herstellung von kristallinem 1,6-bis-Äthylenimino-1,6-didesoxy-3,4-isopropyliden-D-mannit.Process for the preparation of crystalline 1,6-bis-ethylenimino-1,6-dideoxy-3 , 4-isopropylidene-D-mannitol The invention relates to a process for the preparation of crystalline 1,6-bis-ethyleneimino-1,6-dideoxy-3,4-isopropylidene-D-mannitol.
Es wurde bereits vorgeschlagen, durch Umsetzung von 1,2 - 5,6 - Dianhydro - 3 ,4 - isopropyliden - D - mannit mit Äthylenimin 1,6-bis-Äthylenimino-1,6-didesoxy-3,4-isopropyliden-D-mannit herzustellen, wobei letzteres nicht in kristalliner, sondern sirupöser instabiler Form anfiel. It has already been suggested by reacting 1,2-5,6-dianhydro - 3, 4 - isopropylidene - D - mannitol with ethylenimine 1,6-bis-Äthylenimino-1,6-dideoxy-3,4-isopropylidene-D-mannitol to produce, the latter not being crystalline, but rather syrupy unstable Form arose.
Zum Stand der Technik gehört weiterhin das in J. Chem. Soc., London, 1957, S. 805 bis 809, beschriebene Verfahren der Herstellung von 1,6-bis-Äthylenimino-1,6-didesoxy-3,4-isopropyliden-D-mannit aus den obengenannten Ausgangsprodukten, wobei zur Entfernung der Äthyleniminspuren ein Verdampfen mit Methanol vorgeschlagen wurde. Aber auch dieses Verfahren führte unerwünschterweise zu einem sirupartigen Produkt, welches binnen einiger Tage zu einem in Wasser unlöslichen Polymer erstarrte. Die Kristallisation wird durch die Gegenwart von Äthylenimin und flüchtigen Nebenprodukten verhindert. Diese können weder durch einfaches Eindampfen noch durch Destillation mit Methanol oder anderen Alkoholen entfernt werden. The prior art also includes that in J. Chem. Soc., London, 1957, pp. 805 to 809, described process for the preparation of 1,6-bis-ethylenimino-1,6-dideoxy-3,4-isopropylidene-D-mannitol from the abovementioned starting materials, with the removal of traces of ethyleneimine evaporation with methanol has been suggested. But this procedure also led undesirably to a syrupy product, which within a few days a polymer insoluble in water solidified. The crystallization is caused by the Prevents the presence of ethyleneimine and volatile by-products. these can neither by simple evaporation nor by distillation with methanol or others Alcohols are removed.
Es wurde nun ein Verfahren zur Herstellung von kristallinem 1,6 - bis - Äthylenimino - 1,6 - didesoxy-3,4-isopropyleniden-D-mannit durch Umsetzung von 1,2 - 5,6 - Dianhydro - 3,4- isopropyliden - 1) - mannit mit Äthylenimin, Entfernung des überschüssigen Äthylenimins durch Destillation, anschließende Zugabe eines organischen Lösungsmittels zu dem Reaktionsprodukt und Abdestillieren dieses Lösungsmittels gefunden, das dadurch gekennzeichnet ist, daß als organisches Lösungsmittel ein hydroxylgruppenfreies Lösungsmittel verwendet wird. There has now been a process for the production of crystalline 1,6 - bis - Ethylenimino - 1,6 - dideoxy-3,4-isopropylenidene-D-mannitol by reaction of 1,2 - 5,6 - dianhydro - 3,4 - isopropylidene - 1) - mannitol with ethyleneimine, removal of the excess ethyleneimine by distillation, then adding an organic Solvent to the reaction product and distilling off this solvent found, which is characterized in that as an organic solvent hydroxyl-free solvent is used.
Bei der praktischen Durchführung des Verfahrens hat es sich als zweckmäßig erwiesen, den nach der Entfernung des überschüssigen Äthylenimins in dem hydroxylgruppenfreien Lösungsmittel aufgenommenen Rückstand wiederholt so lange zu destillieren, bis das Destillat neutral abläuft. Aus der erhaltenen Lösung kristallisiert das Produkt unmittelbar aus; es kann aber auch mit anderen Lösungsmitteln, in denen es schwer löslich ist, gefällt werden. It has proven to be useful in the practical implementation of the procedure proved that after the removal of the excess ethyleneimine in the hydroxyl group-free Solvent absorbed residue to be distilled repeatedly until the The distillate runs off neutrally. The product crystallizes from the solution obtained immediately off; But it can also be used with other solvents in which it is difficult is soluble, to be felled.
Als Lösungsmittel zur Durchführung der azeotropen Destillation kann man vorteilhaft Benzol oder einen chlorierten Kohlenwasserstoff verwenden. Zum Fällen des Produktes ist es vorteilhaft, Äther zu verwenden. Can be used as a solvent for carrying out the azeotropic distillation it is advantageous to use benzene or a chlorinated hydrocarbon. For felling of the product it is advantageous to use ether.
Das kristalline Produkt ist frei von Feuchtigkeit und Säurespuren zu lagern. The crystalline product is free from moisture and traces of acids to store.
Es ist weiterhin vorteilhaft, die Reaktion unter wasserfreien Bedingungen und mit wasserfreien Lö- sungsmitteln durchzuführen, da durch diese Maßnahmen die Isolierung und weitere Reinigung des Produktes erleichtert wird. Um Nebenreaktionen des Äthylenimins - z. B. Polymerisation - entgegenzuwirken, wird empfohlen, die Reaktion in Gegenwart von Alkalimetallen, Alkalihydroxyden oder tertiären Aminen durchzuführen. It is also advantageous to carry out the reaction under anhydrous conditions and with anhydrous solvent to carry out solvents, since these measures the Isolation and further purification of the product is facilitated. To side reactions of ethylene imine - z. B. Polymerization - to counteract the Reaction in the presence of alkali metals, alkali hydroxides or tertiary amines perform.
Beispiel 1 In 27 g 1,2-5,6- Dianhydro -3,4 - isopropyliden-D-mannit werden 40 ml Äthylenimin eingetragen. Example 1 In 27 g of 1,2-5,6-dianhydro -3,4-isopropylidene-D-mannitol 40 ml of ethyleneimine are entered.
Während der exothermen Reaktion wird eine Temperatur von 45"C beibehalten. Nachdem keine weitere Wärmeentwicklung stattfindet, wird der größte Teil des Äthylenimin-Überschusses unter vermindertem Druck abgetrieben. Nach Zugabe von 3 30 ml wasserfreiem Benzol wird im Vakuum destilliert, bis das Destillat neutral abläuft. Die zurückgebliebene sirupartige Benzollösung wiegt etwa 50 g. Die Lösung wird 24 Stunden lang im Kühlschrank gehalten, dann werden die ausgeschiedenen Kristalle filtriert und im Vakuum über Lauge getrocknet. Es werden 10 g 1,6-bis-Äthylenimino -1 ,6-didesoxy-3,4-isopropyliden- D-mannit erhalten. Schmp. 91 bis 92"C. Spezifisches Drehungsvermögen in Chloroform: [d;]20 = +26,12°; c = 1,835.A temperature of 45 ° C. is maintained during the exothermic reaction. When no further heat generation takes place, most of the ethyleneimine excess becomes driven off under reduced pressure. After adding 3 30 ml of anhydrous benzene is distilled in vacuo until the distillate is neutral. The one left behind syrupy benzene solution weighs about 50 g. The solution is kept in the refrigerator for 24 hours held, then the precipitated crystals are filtered and vacuumed over Lye dried. There are 10 g of 1,6-bis-Äthylenimino -1, 6-dideoxy-3,4-isopropylidene D-mannitol obtain. M.p. 91 to 92 "C. Specific rotatory power in chloroform: [d;] 20 = + 26.12 °; c = 1.835.
Analysenergebnisse in O/,: C 57,45, H 8,84, N 10,27; Berechnete Werte: C 57,40, H 8,80, N 10,30.Analysis results in O / I: C 57.45, H 8.84, N 10.27; Calculated values: C 57.40, H 8.80, N 10.30.
Das Produkt ist in Wasser, in Alkoholen, Aceton, Benzol, chlorierten Kohlenwasserstoffen, Äthanolamin gut löslich. Es löst sich kaum in Äther und Dioxan. The product is chlorinated in water, in alcohols, acetone, benzene Hydrocarbons, ethanolamine readily soluble. It hardly dissolves in ether and dioxane.
Beispiel 2 Zu 27 g 1,2-5,6- Dianhydro -3,4- isopropyliden-D-mannit werden 40ml Äthylenimin und 0,1 g Natrium hinzugefügt. Es wird wie im Beispiel 1 weitergearbeitet und 19 g 1, 6-bis-Äthylenimino-1, 6-didesoxy-3,4-isopropyliden-n-mannit erhalten. Schmp. Example 2 To 27 g of 1,2-5,6-dianhydro -3,4-isopropylidene-D-mannitol 40ml ethyleneimine and 0.1 g sodium are added. It will be like in example 1 worked further and 19 g of 1, 6-bis-Äthylenimino-1, 6-dideoxy-3,4-isopropylidene-n-mannitol obtain. M.p.
92"C.92 "C.
Beispiel 3 Zu 27 g 1,2-5,6- Dianhydro -3,4 - isopropyliden-D-mannit werden 40 mol Äthylenimin und 0,1 g Natrium hinzugefügt. Nach Beendigung der exothermen Reaktion wird der größte Teil des Äthyleniminüberschusses im Vakuum abdestilliert, dann werden 3 30 ml Dichloräthan zugesetzt. Nach wiederholter Destillation unter vermindertem Druck wird die erhaltene dickflüssige Lösung mit 100 ml Äther versetzt, worauf nach einigem Stehen Kristalle ausfallen, die nach 24 Stunden Kühlen isoliert werden. 15 g des 1,6-bis -Äthylenimino - 1,6-didesoxy-3,4-isopropyliden D-mannits werden erhalten. Schmp. 92"C. Example 3 To 27 g of 1,2-5,6-dianhydro -3,4-isopropylidene-D-mannitol 40 mol of ethyleneimine and 0.1 g of sodium are added. After the exothermic Reaction, most of the ethyleneimine excess is distilled off in vacuo, then 3 30 ml of dichloroethane are added. After repeated Distillation under 100 ml of ether are added to the viscous solution obtained under reduced pressure, whereupon crystals precipitate after standing for some time, which are isolated after cooling for 24 hours will. 15 g of 1,6-bis-ethylenimino-1,6-dideoxy-3,4-isopropylidene D-mannitol will get. M.p. 92 "C.
Claims (2)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HUGO000635 | 1958-07-07 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1241831B true DE1241831B (en) | 1967-06-08 |
Family
ID=94733438
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEG27455A Pending DE1241831B (en) | 1958-07-07 | 1959-07-06 | Process for the preparation of crystalline 1, 6-bis-AEthylenimino-1, 6-dideoxy-3, 4-isopropylidene-D-mannitol |
Country Status (3)
| Country | Link |
|---|---|
| DE (1) | DE1241831B (en) |
| GB (1) | GB864235A (en) |
| SE (1) | SE220350C1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0363582A1 (en) * | 1988-08-10 | 1990-04-18 | Bayer Ag | Substituted dioxolanes |
-
1959
- 1959-07-06 DE DEG27455A patent/DE1241831B/en active Pending
- 1959-07-07 GB GB23353/59A patent/GB864235A/en not_active Expired
- 1959-07-07 SE SE639859A patent/SE220350C1/sv unknown
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0363582A1 (en) * | 1988-08-10 | 1990-04-18 | Bayer Ag | Substituted dioxolanes |
Also Published As
| Publication number | Publication date |
|---|---|
| SE220350C1 (en) | 1968-05-07 |
| GB864235A (en) | 1961-03-29 |
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