DE1065401B - Process for the preparation of monooxytriethers - Google Patents
Process for the preparation of monooxytriethersInfo
- Publication number
- DE1065401B DE1065401B DENDAT1065401D DE1065401DA DE1065401B DE 1065401 B DE1065401 B DE 1065401B DE NDAT1065401 D DENDAT1065401 D DE NDAT1065401D DE 1065401D A DE1065401D A DE 1065401DA DE 1065401 B DE1065401 B DE 1065401B
- Authority
- DE
- Germany
- Prior art keywords
- mol
- polyhydric alcohol
- preparation
- solvent
- excess
- 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 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 6
- KCXMKQUNVWSEMD-UHFFFAOYSA-N Benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 4
- -1 monooxy Chemical group 0.000 claims description 4
- 125000005429 oxyalkyl group Chemical group 0.000 claims description 4
- 125000003342 alkenyl group Chemical group 0.000 claims description 3
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- WXZMFSXDPGVJKK-UHFFFAOYSA-N 2,2-bis(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- WACQLQIAUWURGA-UHFFFAOYSA-N 3-hydroxy-2,2-bis(hydroxymethyl)propanoic acid Chemical compound OCC(CO)(CO)C(O)=O WACQLQIAUWURGA-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 150000001350 alkyl halides Chemical group 0.000 description 2
- 150000001502 aryl halides Chemical class 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- YXCDZXGJZDGMEP-UHFFFAOYSA-N 4-hydroxy-3,3-bis(hydroxymethyl)butan-2-one Chemical compound CC(=O)C(CO)(CO)CO YXCDZXGJZDGMEP-UHFFFAOYSA-N 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N Allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- UVJTVECQHWJRQG-UHFFFAOYSA-N C1(=CC=CC=C1)C(O)C(CO)(CO)CO Chemical compound C1(=CC=CC=C1)C(O)C(CO)(CO)CO UVJTVECQHWJRQG-UHFFFAOYSA-N 0.000 description 1
- 241000546339 Trioxys Species 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N iso-propanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Gegenstand des älteren deutschen Patents 1 021 346 ist ein Verfahren zur Herstellung von Monooxydiäthern, das darin besteht, 1 Mol eines mehrwertigen Alkohols mit drei primären Oxyalkylgruppen an einem Kohlenstoffatom mit mindestens 2 Mol eines Alkyl- oder Arylhalogenids oder 1 Mol eines Dioxymonoäthers eines solchen mehrwertigen Alkohols mit mindestens 1 Mol eines Alkyl- oder Arylhalogenids, jeweils in Gegenwart einer äquivalenten Menge eines Alkylihydroxyds, vorzugsweise in Gegenwart eines Lösungsmittels, insbesondere des Monooxydiäthers, der hergestellt werden soll, umzusetzen. The subject of the earlier German patent 1 021 346 is a process for the production of mono-oxide dieters, which consists in 1 mole of a polyhydric alcohol having three primary oxyalkyl groups on one carbon atom with at least 2 moles of an alkyl or aryl halide or 1 mole of a dioxymonoether such polyhydric alcohol with at least 1 mole of an alkyl or aryl halide, in each case in the presence an equivalent amount of an alkyl hydroxide, preferably in the presence of a solvent, in particular of the mono-oxide diet to be produced.
Es wurde nun gefunden, daß sich mehrwertige Alkohole mit vier Oxyalkylgruppen an einem Kohlenstoffatom oder Trioxymonoäther oder Dioxydiäther eines solchen mehrwertigen Alkohols entsprechend umsetzen lassen, so daß man Monooxytriäther erhält. Das neue Verfahren besteht somit darin, ein Mol eines mehrwertigen Alkohols mit vier Oxyalkylgruppen an einem Kohlenstoffatom, insbesondere Pentaerythrit, ferner z. B. 3,3,3-Trimethylolisopropanol und 2,2,2-Trimethylol-l-phenyläthanol, oder eines Trioxymonoäthers oder eines Dioxydiäthers eines solchen mehrwertigen Alkohols mit mindestens 3 Mol bzw. mindestens 2 Mol bzw. mindestens 1 Mol eines Alkenyl- oder Benzylhalogenids in Gegenwart einer äquivalenten Menge eines Alkalihydroxyds, vorzugsweise in Gegenwart eines Lösungsmittels, umzusetzen.It has now been found that polyhydric alcohols with four oxyalkyl groups on one carbon atom or let trioxymonoether or dioxydiether of such a polyhydric alcohol react accordingly, so that one obtains monooxy triether. The new process thus consists in using one mole of a polyhydric alcohol with four oxyalkyl groups on one carbon atom, in particular pentaerythritol, further z. B. 3,3,3-trimethyl isopropanol and 2,2,2-trimethylol-1-phenylethanol, or of a trioxy monoether or a dioxydiether of such a polyhydric alcohol with at least 3 mol or at least 2 moles or at least 1 mole of an alkenyl or benzyl halide in the presence of one equivalent amount of an alkali hydroxide, preferably in the presence of a solvent to implement.
Als geeignete Alkenyl- bzw. Benzylhalogenide sind z. B. Allylchlorid und -bromid und Benzylchlorid und -bromid zu nennen.Suitable alkenyl or benzyl halides are, for. B. allyl chloride and bromide and benzyl chloride and to call bromide.
Auch bei diesem Verfahren arbeitet man vorteilhaft in Gegenwart des Monooxytriäthers als Lösungsmittel, der hergestellt werden soll.In this process too, it is advantageous to work in the presence of the monooxytriether as a solvent, the should be produced.
Zu einer Mischung aus 272 g Pentaerythrit (2 Mol) und 747 g 45°/0iger Natronlauge (6 Mol + 96 g Überschuß) gibt man unter Rühren bei 80 bis 1000C 641 g Allylchlorid (6.MoI + 182 g Überschuß) in dem Maße, wie das Allylchlorid verbraucht wird.To a mixture of 272 g of pentaerythritol (2 moles) and 747 g of 45 ° / 0 sodium hydroxide is added (6 mol + 96 g excess) with stirring at 80 to 100 0 C 641 g of allyl chloride (6.MoI + 182 g excess) as the allyl chloride is consumed.
Die Eintragung dauert etwa 6 bis 8 Stunden. Dann wird Xylol zu der Reaktionsmischung gegeben und das Wasser azeotrop abdestilliert. Der Rückstand wird vom Natriumchlorid abfiltriert und das Filtrat durch fraktionierende Destillation unter vermindertem Druck zerlegt. Zunächst destilliert der Überschuß von Allylchlorid und Xylol ab. Man erhält 470 g Rohäthergemisch. Dieses fraktioniert man wie folgt:Registration takes about 6 to 8 hours. Then xylene is added to the reaction mixture and that Water distilled off azeotropically. The residue is filtered off from the sodium chloride and the filtrate by fractionating Distillation decomposed under reduced pressure. First, the excess of allyl chloride and distilled Xylene off. 470 g of a crude ether mixture are obtained. This is fractionated as follows:
329 g = 70 % Monooxytriallyläther329 g = 70% monooxytriallyl ether
Siedepunkt 126 bis 130°C/l-2 mm HgBoiling point 126 to 130 ° C / l-2 mm Hg
118 g = 25% Dioxydiallyläther118 g = 25% dioxydiallyl ether
Siedepunkt 139 bis 144°C/l-2 mm HgBoiling point 139 to 144 ° C / l-2 mm Hg
Verfahren zur Herstellung
von MonooxytriäthernMethod of manufacture
of monooxytriethers
Anmelder:Applicant:
Farbenfabriken Bayer Aktiengesellschaft,
LeverkusenPaint factories Bayer Aktiengesellschaft,
Leverkusen
Beanspruchte Priorität:Claimed priority:
V. St. v. Amerika, vom 25. Juni 1957V. St. v. America, June 25, 1957
und Kanada vom 25. Juni 1957and Canada dated June 25, 1957
Dr. Karl Raichle und Dr. Wilhelm Krey,Dr. Karl Raichle and Dr. Wilhelm Krey,
Krefeld-Uerdingen,
sind als Erfinder genannt wordenKrefeld-Uerdingen,
have been named as inventors
5g= 1 °/0 Trioxymonoallyläther5g = 1 ° / 0 Trioxymonoallyläther
Siedepunkt 163 bis 170°C/l-2 mm Hg
15 g = 3% Rückstand.Boiling point 163 to 170 ° C / l-2 mm Hg
15 g = 3% residue.
Bei der Durchführung der Reaktion sind Variationen möglich. So wird die Reaktionszeit fast auf die Hälfte verkürzt, wenn man Pentaerythrittriallyläther (rein oder im Gemisch mit Di- und Monoäther) als Lösungsmittel zusetzt (etwa 100 bis 400 g). In diesem Fall kann das Ätznatron auch wasserfrei in feinverteilter Form angewandt werden. Hierdurch vereinfacht man die Aufarbeitung, da gegebenenfalls auf die Entfernung der geringen Mengen des Reaktionswassers verzichtet werden kann.Variations are possible in carrying out the reaction. This cuts the response time by almost half shortened if you use pentaerythritol triallyl ether (pure or mixed with di- and monoethers) as the solvent added (about 100 to 400 g). In this case, the caustic soda can also be used in finely divided form anhydrous will. This simplifies the work-up, since if necessary the removal of the small amounts of the water of reaction can be dispensed with.
Des weiteren lassen sich auch Mono- und Diäther des Pentaerythrits entsprechend umsetzen und auf diese Weise gemischte Triäther herstellen.Furthermore, mono- and dieters of pentaerythritol can also be implemented accordingly and on them Make a wise mixed triether.
Zu einer Lösung aus 226 g (1 Mol) Trioxypentaerythritmonobenzyläther (Kp. 0>4 = 1900C) in 300 g Monooxytrimethylolpropandiallyläther gibt man unter Rühren bei 60 bis 8O0C 96 g Ätznatron (2MoI + 16 g Überschuß)To a solution of 226 g (1 mol) Trioxypentaerythritmonobenzyläther (Kp. 0> 4 = 190 0 C) in 300 g Monooxytrimethylolpropandiallyläther are added with stirring at 60 to 8O 0 C. 96 g of caustic soda (2MoI + 16 g excess)
und 183 g Allylchlorid (2 Mol + 3Ig Überschuß). Nach Zugabe des ganzen Alrylchlorids nach etwa 1 bis 2 Stunden wird das Rühren bei 60 bis 8O0C noch etwa für eine Stunde fortgesetzt. Dann wird die Mischung mit Salzsäure neutralisiert und mit Wasser gewaschen. Die organische Schicht wird abgetrennt und fraktioniert. Man erhält bei Atmosphärendruck 20 g unverändertes Allylchlorid und bei vermindertem Druck zunächst Monooxytrimethylolpropandiallyläther. Bei 180 bis 1850C/ 3 mm destillieren 270 bis 280 g Monooxypentaerythrit-and 183 g of allyl chloride (2 mol + 3Ig excess). After addition of the whole Alrylchlorids after about 1 to 2 hours, stirring at 60 to 8O 0 C is still about continued for one hour. Then the mixture is neutralized with hydrochloric acid and washed with water. The organic layer is separated and fractionated. 20 g of unchanged allyl chloride are obtained at atmospheric pressure and initially monooxytrimethylolpropane diallyl ether is obtained under reduced pressure. At 180 to 185 0 C / 3 mm, 270 to 280 g of monooxypentaerythritol distill
909 628/409909 628/409
monobenzyldiallyläther ab. Die Hydroxylzahl des Produktes ist 188 bis 189 (errechnet 186).monobenzyldiallyl ether. The hydroxyl number of the product is 188 to 189 (calculated 186).
■ . ; i Beispiel 3■. ; i Example 3
•C i- ■ ■ ■.'..■ • C i- ■ ■ ■. '.. ■
Zu' 430 g (2 Mol) Dioxypentaerythritdiallyläther, erhalten nach Beispiel! als Nebenprodukt, gibt man 96 g Natriumhydroxydpulver (2 Mol + 16 g Überschuß). Die Mischung wird unter Rühren auf 60 bis 9O0C erhitzt. Man tropft im Verlauf von 3 bis 4 Stunden 302 g Benzyl- ίο chlorid (2 Mol + 50 g Überschuß) hinzu. Das Rühren wird 1 Stunde bei dieser Temperatur fortgesetzt. Das zurückbleibende Natriumchlorid wird abfutriert, das Filtrat mit Wasser gewaschen und fraktioniert. Man erhält aus 630 g Rohprodukt 560 g Monooxypentaerythritmonobenzyldiallyläther, identisch dem Produkt nach Beispiel 2. Rückstand 50 g.To '430 g (2 mol) of dioxypentaerythritol diallyl ether, obtained according to the example! 96 g of sodium hydroxide powder (2 mol + 16 g excess) are added as a by-product. The mixture is heated with stirring at 60 to 9O 0 C. 302 g of benzyl chloride (2 mol + 50 g excess) are added dropwise in the course of 3 to 4 hours. Stirring is continued at this temperature for 1 hour. The remaining sodium chloride is filtered off, the filtrate is washed with water and fractionated. From 630 g of crude product, 560 g of monooxypentaerythritol monobenzyldiallyl ether, identical to the product according to Example 2, are obtained. 50 g of residue.
Claims (1)
'""2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man als Lösungsmittel den Monooxytriäther verwendet, der hergestellt werden soll.1. A process for the preparation of Monooxytriäthern, characterized in that 1 mol of a polyhydric alcohol with four oxyalkyl groups on one carbon atom or a trioxymonoether or a dioxydiether of such a polyhydric alcohol with at least 3 mol or at least 2 mol or at least 1 mol of an alkenyl - Or benzyl halide in the presence of an equivalent amount of an alkali metal hydroxide, preferably in the presence of a solvent.
'"" 2. Process according to Claim 1, characterized in that the solvent used is the monooxy triether which is to be prepared.
Deutsches Patent Nr. 1 021 346.Legacy Patents Considered:
German Patent No. 1 021 346.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1065401B true DE1065401B (en) | 1959-09-17 |
Family
ID=591748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT1065401D Pending DE1065401B (en) | Process for the preparation of monooxytriethers |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1065401B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3195975A (en) * | 1961-08-10 | 1965-07-20 | Montedison Spa | Tri-methylol propane diallyl ether treatment of polyolefin-polymeric nitrogenous compound mixtures and fibers and product thereof |
| US3456019A (en) * | 1966-04-07 | 1969-07-15 | British Petroleum Co | Ether alcohols |
-
0
- DE DENDAT1065401D patent/DE1065401B/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3195975A (en) * | 1961-08-10 | 1965-07-20 | Montedison Spa | Tri-methylol propane diallyl ether treatment of polyolefin-polymeric nitrogenous compound mixtures and fibers and product thereof |
| US3456019A (en) * | 1966-04-07 | 1969-07-15 | British Petroleum Co | Ether alcohols |
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