DE850752C - Process for the preparation of 1,3-oxido-2-oxymethyl-2-halomethylpropane - Google Patents
Process for the preparation of 1,3-oxido-2-oxymethyl-2-halomethylpropaneInfo
- Publication number
- DE850752C DE850752C DER152A DER0000152A DE850752C DE 850752 C DE850752 C DE 850752C DE R152 A DER152 A DE R152A DE R0000152 A DER0000152 A DE R0000152A DE 850752 C DE850752 C DE 850752C
- Authority
- DE
- Germany
- Prior art keywords
- oxido
- oxymethyl
- preparation
- halomethylpropane
- chem
- 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 5
- 238000002360 preparation method Methods 0.000 title claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229940059574 pentaerithrityl Drugs 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CHUGKEQJSLOLHL-UHFFFAOYSA-N 2,2-Bis(bromomethyl)propane-1,3-diol Chemical compound OCC(CO)(CBr)CBr CHUGKEQJSLOLHL-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical class CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- 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 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000006798 ring closing metathesis reaction Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
- C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D305/06—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms 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 atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von 1, 3-Oxido-2-oxymethyl-2-halogenmethylpropan Gegenstand der Erfindung ist ein Verfahren zur Herstellung von 1, 3-Oxido-2-oxvmethyl-2-halogenmethylpropan.Process for the preparation of 1, 3-oxido-2-oxymethyl-2-halomethylpropane The invention relates to a process for the preparation of 1,3-oxido-2-oxvmethyl-2-halomethylpropane.
Von der allgemeinen Formel (in der \ Halogen bedeutet) sich ableitende Abkömmlinge des Tetramethylmethans, die i, 3-Oxido-2-oxymethyl-2-halogenmethyIpropane, sind bisher noch nicht bekannt. Lediglich die um 1 @@ol Halogenwasserstoff ärmere Verbindung, das doppelte Anitv(lrid desPentaerythrits,wird als 2, 6-l)ioxaspiro-3, 3-heptan in der Literatur beschrieben. Nach Angaben von S. F. M a r r i a n geht man zur Herstellung dieser Verbindung von dem Pentaerythritdibromhvdrin aus und setzt dasselbe bei erhöhter Temperatur mit in einem vielfachen Überschuß angewendeter alkoholischer Kalilauge in 2o- bis 25O/-oiger Ausbeute um.From the general formula (in which \ halogen means) derived derivatives of tetramethylmethane, the i, 3-oxido-2-oxymethyl-2-halogenomethyl propane, are not yet known. Only the compound less by 1 @@ ol hydrogen halide, the double anion (iride des pentaerythritol, is described in the literature as 2,6-l) ioxaspiro-3,3-heptane. According to SF M arrian, this compound is prepared from pentaerythritol dibromohydrin and reacted at elevated temperature with alcoholic potassium hydroxide solution, which is used in a multiple excess, in a yield of 20 to 250%.
Ferner ist es bekamst, von Trihalogen.monooxydürivaten des Tetramethylmethans ausgehend, unter einseitiger RingschlußbilJung Verbindungen herzustellen, die neben einem sauerstoffhaltigen Ring Halogen in der Seitenkette enthaltene und in denen das Halogen infolge Abwesenheit einer weiteren reaktionsbereiten Gruppe, wie Hydroxyl, auch unter dem Einfluß starker Alkalien nicht abgespalten wird, so daß die Herstellung dieser Verbindungen. keine besonderen Schwierigkeiten bereitet.It is also obtained from Trihalogen.monooxydürivaten of tetramethylmethane starting to establish connections with one-sided ring closure formation, the next an oxygen-containing ring halogen contained in the side chain and in which the halogen due to the absence of another reactive group, such as hydroxyl, also under is not split off under the influence of strong alkalis, so making these connections. does not cause any particular difficulties.
Die Herstellung einer Verbindung, die im Molekül neben Halogen noch eine Hydroxylgruppe enthält, mußte dagegen, da schon die relativ einfach vorzunehmende Abspaltung des gesamten Halogenwasserstoffes aus dem Pentaerythritdtibromhydrin narr zu 20 bis 25 % den gewünschten Verlauf nimmt, als sehr schwer durchführbar erscheinen. Bei der Gleichartigkeit der beiden Halogenatome im Dihalogenhydrin und der Anwesenheit zweier Hyd.roxylgruppen war es nicht zu erwarten, daß bei nur einseitiger Ringbildung ein verhältnismäßig einfacher Reaktionsverlauf stattfinden würde, vielmehr mußte die Bildung schwer angenommen werden.The production of a compound that is in the molecule in addition to halogen contains a hydroxyl group, on the other hand, had to be done, since the one that is relatively easy to carry out All of the hydrogen halide is split off from the pentaerythritol tibromohydrin foolishly to 20 to 25% takes the desired course, as very difficult to carry out appear. Given the similarity of the two halogen atoms in dihalohydrin and the presence of two hydroxyl groups, it was not to be expected that only one-sided Rather, ring formation would take place a relatively straightforward course of the reaction education had to be accepted with difficulty.
Es wurde nun die überraschende Feststellung gemacht, daß man dennoch die bisher unbekannten i, 3-Oxido-2-oxymet'hyl-2-halogenmethylpropane in reiner Form gewinnen kann, wenn man Dihalogenhydrine des Tetrametfhylolmethans in der Kälte mit der molaren Menge Älkal,ialkoholat, insbesondere den Alkoholaten höhermolekularer Alkohole, zur Umsetzung bringt und das entstehende Reaktionsprodukt durch Destillation unter vermindertem Druck isoliert.The surprising finding has now been made that one nevertheless the hitherto unknown i, 3-oxido-2-oxymethyl-2-halomethylpropane in pure Can gain shape by taking dihalohydrins of tetramethylolmethane in the cold with the molar amount of alkali, alkoxide, especially the alcoholates of higher molecular weight Alcohols, and the resulting reaction product by distillation isolated under reduced pressure.
Die neuen Verbindungen können als solche oder als Zwischenprodukte, beispielsweise zur Herstellung von Arzneimitteln und infolge ihrer Wasserlöslichkeit zur Herstellung von Arzneimittelzubereitungen, Verwendung finden. Beispiel 26,2 g Pentaerythritdibromhydrin werden in 50 ccm i-Propylalkohol gelöst. Unter Rühren und Kühlen wird eine Lösung von 2,3 g Natrium in i ,5o ccm i-Propylalkohol zugetropft. Die i-Propylatlösung muß, um ein Auskristallisieren dies Natriuma.lkoholats zu verhindern, schwach angewärmt werden. Nach etwa io Stunden ist die Umsetzung beendet. Man saugt nun vom abgeschiedenen Natriumbromid ab und destilliert vom Filtrat den größten Teil des Alkohols ab. Den Rückstand nimmt man mit wenig Wasser und Benzol auf. Die wäßrige Schicht wird noch einige Male mit Benzol ausgeschüttelt, die vereinigten lknzolauszüge werden eingedampft, und der Rückstand wird im Vakuum destilliert. Das so erhaltene 1, 3-Oxido-2-oxymethyl-2-brommethylpropan geht als dickes, farbloses 01 vom Siedepunkt 105 bis io9° (i bis 2 mm) über. Es ist in Wasser, Alkohol, Benzol und Äther leicht, in Benzin schwer löslich. Beim Behandeln der wäßrigen Lösung mit Halogenwasserstoffsäuren kristallisieren unter Aufspaltung der Sauerstoffbrücke die entsprechenden Dihalogenhydrine aus; bei Anwendung von Bromwasserstoffsäure bildet sich das Dibromhydrin zurück.The new compounds can be used as such or as intermediates, for example for the production of medicaments and, owing to their solubility in water, for the production of medicament preparations. Example 26.2 g of pentaerythritol dibromohydrin are dissolved in 50 cc of i-propyl alcohol. A solution of 2.3 g of sodium in 1.5o ccm of i-propyl alcohol is added dropwise with stirring and cooling. The i-propylate solution must be warmed slightly to prevent this sodium alcoholate from crystallizing out. The reaction has ended after about 10 hours. The sodium bromide which has separated out is then suctioned off and most of the alcohol is distilled off from the filtrate. The residue is taken up with a little water and benzene. The aqueous layer is extracted a few more times with benzene, the combined extracts of oil are evaporated and the residue is distilled in vacuo. The thus obtained 1, 3-oxido-2-oxymethyl-2-brommethylpropan is as a thick, colorless 01 of boiling point 105 to about io9 ° (i to 2 mm). It is easily soluble in water, alcohol, benzene and ether, but poorly soluble in gasoline. When the aqueous solution is treated with hydrohalic acids, the corresponding dihalohydrins crystallize out with splitting of the oxygen bridge; when hydrobromic acid is used, the dibromohydrin is regressed.
DieAusbeute an i, 3-Oxido-2-oxymethyl-2-brommethylpropan beträgt io bis 12 g, das sind 6o bis 66 % der Theorie.The yield of i, 3-oxido-2-oxymethyl-2-bromomethylpropane is io up to 12 g, that is 60 to 66% of theory.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DER152A DE850752C (en) | 1949-10-26 | 1949-10-26 | Process for the preparation of 1,3-oxido-2-oxymethyl-2-halomethylpropane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DER152A DE850752C (en) | 1949-10-26 | 1949-10-26 | Process for the preparation of 1,3-oxido-2-oxymethyl-2-halomethylpropane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE850752C true DE850752C (en) | 1952-09-29 |
Family
ID=7394984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DER152A Expired DE850752C (en) | 1949-10-26 | 1949-10-26 | Process for the preparation of 1,3-oxido-2-oxymethyl-2-halomethylpropane |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE850752C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2794027A (en) * | 1957-05-28 | Tkeparation | ||
| DE1030353B (en) * | 1954-06-01 | 1958-05-22 | Hercules Powder Co Ltd | Process for the preparation of 3,3-bis (chloromethyl) oxacyclobutane |
| DE1030352B (en) * | 1954-01-28 | 1958-05-22 | Hercules Powder Co Ltd | Process for the preparation of 3,3-bis (chloromethyl) oxacyclobutane |
-
1949
- 1949-10-26 DE DER152A patent/DE850752C/en not_active Expired
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2794027A (en) * | 1957-05-28 | Tkeparation | ||
| DE1030352B (en) * | 1954-01-28 | 1958-05-22 | Hercules Powder Co Ltd | Process for the preparation of 3,3-bis (chloromethyl) oxacyclobutane |
| DE1030353B (en) * | 1954-06-01 | 1958-05-22 | Hercules Powder Co Ltd | Process for the preparation of 3,3-bis (chloromethyl) oxacyclobutane |
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