DE1593867B - Process for the production of 2,2 dimethyl 2 sila 1,4 dioxane excretion from 1250448 - Google Patents
Process for the production of 2,2 dimethyl 2 sila 1,4 dioxane excretion from 1250448Info
- Publication number
- DE1593867B DE1593867B DE1593867B DE 1593867 B DE1593867 B DE 1593867B DE 1593867 B DE1593867 B DE 1593867B
- Authority
- DE
- Germany
- Prior art keywords
- dimethyl
- sila
- dioxane
- bromomethyl
- excretion
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 title claims description 3
- 238000000034 method Methods 0.000 title description 6
- 230000036826 Excretion Effects 0.000 title 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 title 1
- 230000029142 excretion Effects 0.000 title 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- -1 dimethyl (bromomethyl) Chemical group 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- HRAPKEROOPNSTP-UHFFFAOYSA-N OCCO[Si](CBr)(C)C Chemical compound OCCO[Si](CBr)(C)C HRAPKEROOPNSTP-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 4
- 238000005886 esterification reaction Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- SPPWGCYEYAMHDT-UHFFFAOYSA-N 1,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C(C)C)C=C1 SPPWGCYEYAMHDT-UHFFFAOYSA-N 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N Chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 238000006959 Williamson synthesis reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- CNTRZROSTQPQPP-UHFFFAOYSA-N bromomethyl-ethoxy-dimethylsilane Chemical compound CCO[Si](C)(C)CBr CNTRZROSTQPQPP-UHFFFAOYSA-N 0.000 description 1
- ADBWXBABTGQLNR-UHFFFAOYSA-N bromomethyl-hydroxy-dimethylsilane Chemical compound C[Si](C)(O)CBr ADBWXBABTGQLNR-UHFFFAOYSA-N 0.000 description 1
- XEYDTPFVYTVHTI-UHFFFAOYSA-N bromomethylsilane Chemical compound [SiH3]CBr XEYDTPFVYTVHTI-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- ITKVLPYNJQOCPW-UHFFFAOYSA-N chloro-(chloromethyl)-dimethylsilane Chemical compound C[Si](C)(Cl)CCl ITKVLPYNJQOCPW-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000007700 distillative separation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- VILMUCRZVVVJCA-UHFFFAOYSA-M sodium;2-hydroxyacetate Chemical compound [Na+].OCC([O-])=O VILMUCRZVVVJCA-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- NRTLTGGGUQIRRT-UHFFFAOYSA-N triethylazanium;bromide Chemical compound [Br-].CC[NH+](CC)CC NRTLTGGGUQIRRT-UHFFFAOYSA-N 0.000 description 1
Description
2,2-Dimethyl-2-sila-l,4-dioxan wurde bisher unter Kombination der Äthersynthese nach Williamson und der Chlorsilan-Veresterung mit Mononatriumglycolat aus Dimethyl-(chlormethyl)-chlorsilan hergestellt. Dieses Herstellungsverfahren ist umständlich und wenig ergiebig, da der überwiegende Teil des Glykols an beiden COH-Gruppen gleichermaßen verestert oder veräthert und damit der angestrebten Reaktion, nämlich der Veresterung an einer und Verätherung an der anderen COH-Gruppe, entzogen wird. Hinzu kommt, daß der bei diesem Verfahren erforderliche Glykolüberschuß nur zeitraubend zu entfernen ist und dabei noch mit dem zu gewinnenden Ätherester unter Umesterung reagiert, so daß man nur zwischen 30 und 35% der theoretisch möglichen Ausbeute erzielt.2,2-Dimethyl-2-sila-l, 4-dioxane was previously combined with the Williamson ether synthesis and the chlorosilane esterification with monosodium glycolate from dimethyl (chloromethyl) chlorosilane manufactured. This manufacturing process is cumbersome and not very productive because the majority of the Glycol is esterified equally on both COH groups or etherified and thus the desired reaction, namely the esterification at one and etherification at the other COH group. In addition, in this process required excess glycol is only time consuming to remove and still with the to be obtained Ether ester reacts with transesterification, so that you only get between 30 and 35% of the theoretically possible Yield achieved.
Die Erfindung betrifft ein Verfahren zur Herstellung von 2,2-Dimethyl-2-sila-l,4-dioxan der FormelThe invention relates to a process for the preparation of 2,2-dimethyl-2-sila-1,4-dioxane of the formula
H2C Si
H2C H2C CH3
OH 2 C Si
H 2 CH 2 C CH 3
O
das dadurch gekennzeichnet ist, daß man in Gegenwart eines inerten organischen Lösungsmittels ein Dimethyl-(brommethyl)-alkoxysilan mit der äquimolaren Menge Äthylenglykol zum Dimethyl-(brommethyl)-(hydroxyäthoxy)-silan der Formelwhich is characterized in that one in the presence of an inert organic solvent Dimethyl (bromomethyl) alkoxysilane with an equimolar amount of ethylene glycol to dimethyl (bromomethyl) (hydroxyethoxy) silane the formula
BrCH2 — Si(CH3)2 — O — C2H4 — OHBrCH 2 - Si (CH 3 ) 2 - O - C 2 H 4 - OH
umsetzt und diesem bei erhöhter Temperatur allmählich eine dem Brom stöchiometrisch äquivalente Menge einer tertiären Stickstoffbase zufügt.converts and this gradually a stoichiometrically equivalent to the bromine at elevated temperature Adds amount of a tertiary nitrogen base.
Das Prinzip einer Verätherungsreaktion einer hydroxylgruppenhaltigen Verbindung mit einem Brommethylsilan nach dem SchemaThe principle of an etherification reaction of a hydroxyl group-containing Connection with a bromomethylsilane according to the scheme
= C — OH + BrCH2 — Si ξ= C - OH + BrCH 2 - Si ξ
^C-O-CH2-Si==^ CO-CH 2 -Si ==
ist bekannt. Im Falle der .Verwendung von ausschließlich difunktionellen Reaktionskomponenten hat man dementsprechend eine Kondensation zu Silapolyäthern, hier also von polymeren Oxymethylsilanolestern der allgemeinen Formelis known. In the case of .use of exclusively difunctional reaction components one has accordingly a condensation to silapolyethers, here, therefore, of polymeric oxymethylsilanol esters of the general formula
-EO-CH2- Si(CH3J2 - O - C2H4^-EO-CH 2 - Si (CH 3 J 2 - O - C 2 H 4 ^
zu erwarten. Es ist daher überraschend, daß man statt dessen bei dem erfindungsgemäßen Verfahren in hohen Ausbeuten das cyclische monomere 2,2-Dimethyl-2-sila-l,4-dioxan erhält.expected. It is therefore surprising that instead in the process according to the invention in the cyclic monomeric 2,2-dimethyl-2-sila-1,4-dioxane is obtained in high yields.
Bei der Durchführung des Verfahrens ist eine Destillation des in der ersten Stufe gebildeten Glykolmonoesters des Dimethyl-(brommethyl)-silanols zu unterlassen, da dies zu Verlusten durch innere Umesterung gemäß der ReaktionsgleichungWhen carrying out the process, a distillation of the glycol monoester formed in the first stage is necessary of dimethyl- (bromomethyl) -silanol, as this leads to losses through internal transesterification according to the reaction equation
2BrCH2- Si(CH3)2 — O — C2H4 — OH2BrCH 2 - Si (CH 3 ) 2 - O - C 2 H 4 - OH
BrCH2-Si(CH3)2-O-CH2
BrCH2-Si(CH3)2-O-CH2 BrCH 2 -Si (CH 3 ) 2 -O-CH 2
BrCH 2 -Si (CH 3 ) 2 -O-CH 2
+ HO-C2H4-OH+ HO-C 2 H 4 -OH
führen würde.would lead.
Die Verwendung eines inerten organischen Lösungsmittels ist dadurch bedingt, daß sich bei der Umsetzung festes Salzausscheidet. Zweckmäßigerweise wählt man dieses Lösungsmittel so, daß dessen Siedepunkt es erlaubt, eine hinreichende Geschwindigkeit der schon bei Raumtemperatur merklichen Reaktion zu erreichen, zugleich aber auch eine befriedigende destillative Trennung vom Reaktionsprodukt ermöglicht. The use of an inert organic solvent is due to the fact that the Dictionary solid salt precipitates. Appropriately, this solvent is chosen so that its boiling point it allows a sufficient speed of the reaction, which is noticeable even at room temperature to achieve, but at the same time also enables a satisfactory distillative separation from the reaction product.
Als tertiäre Stickstoffbase zur Bindung des Bromwasserstoffs, der sich bei der Kondensationsreaktion der siliciumgebundenen Brommethylgruppe mit der freien Hydroxylgruppe derselben Molekel unter Ring-Schluß abspaltet, eignet sich vornehmlich das Triäthylamin. As a tertiary nitrogen base to bind the hydrogen bromide that occurs during the condensation reaction the silicon-bonded bromomethyl group with the free hydroxyl group of the same molecule to form a ring splits off, triethylamine is particularly suitable.
Das Verfahrensprodukt eignet sich auf Grund der Eigenschaft, daß sich seine Si — O — C-Bindung verhältnismäßig leicht spalten läßt, ausgezeichnet zur Einführung von Silicium in organische Verbindungen und zur Herstellung von Organopolysiloxanen mit bestimmt dosierten carbofunktionellen Einheiten.The process product is suitable because of the property that its Si - O - C bond is proportionate can be easily cleaved, excellent for introducing silicon into organic compounds and for the production of organopolysiloxanes with precisely dosed carbofunctional units.
Ein Gemisch von 150 g (0,75 Mol) Dimethyl-(brommethyl)-äthoxysilan von 98,1 Gewichtsprozent Reinheit, 46,6 g (0,75MoI) Äthylenglykol und 200 cm3 1,4-Diisopropylbenzol erhitzt man auf 150° C und leitet durch dieses Gemisch 2 Stunden lang einen schwachen Strom von getrocknetem Stickstoff. Dabei werden in einer nachgeschalteten Kühlfalle 34,4 g (0,75 Mol)Äthanol aufgefangen. Zu der hinterbliebenen Lösung von Dimethyl -(brommethyl)-(ß- hydroxyäthoxy)-silan läßt man weiterhin bei 150° C im Verlaufe von 3 Stunden 76 g (0,75 Mol) Triäthylamin tropfen und setzt dann das Erhitzen 3 Stunden lang fort. Das danach ausgefallene Triäthylammoniumbromid filtriert man ab und destilliert das Filtrat beiA mixture of 150 g (0.75 mol) of dimethyl (bromomethyl) ethoxysilane of 98.1 percent by weight purity, 46.6 g (0.75 mol) of ethylene glycol and 200 cm 3 of 1,4-diisopropylbenzene is heated to 150.degree and passing a gentle stream of dried nitrogen through this mixture for 2 hours. In this case, 34.4 g (0.75 mol) of ethanol are collected in a downstream cold trap. 76 g (0.75 mol) of triethylamine are added dropwise to the remaining solution of dimethyl (bromomethyl) ( β-hydroxyethoxy) silane at 150 ° C. over the course of 3 hours, and heating is then continued for 3 hours. The then precipitated triethylammonium bromide is filtered off and the filtrate is distilled
Atmosphärendruck fraktioniert, wobei man als bei Analyse in Gewichtsprozent für C5H12O2Si:Fractionated atmospheric pressure, with the analysis in percent by weight for C 5 H 12 O 2 Si:
135° C übergehende Fraktion 79 g reines 2,2-Dimethyl-135 ° C passing fraction 79 g of pure 2,2-dimethyl
2-sila-l,4-dioxan (Ausbeute ungefähr 80% der Theorie) Berechnet... C 45,4, H 9,1%;2-sila-1,4-dioxane (yield approx. 80% of theory) Calculated ... C 45.4, H 9.1%;
vom Brechungsindex nl° = 1,4288 erhält. gefunden C 45,5, H 9,1%.obtained from the refractive index nl ° = 1.4288. found C 45.5, H 9.1%.
Protonenverhältnis CH2 · CH2 : Si · CH2 · O : Si(CH3)2 Proton ratio CH 2 · CH 2 : Si · CH 2 · O: Si (CH 3 ) 2
Durch kernmagnetische Resonanzmessung bestimmt 4,0 : 2,0 : 6,1Determined by nuclear magnetic resonance measurement 4.0: 2.0: 6.1
Berechnet 4 : 2 : 6Calculates 4: 2: 6
Claims (1)
2-sila-l,4-dioxan der FormelMethod of manufacture
2-sila-l, 4-dioxane of the formula
H2C H2C CH3
OH 2 C Si
H 2 CH 2 C CH 3
O
Family
ID=
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE69412084T2 (en) | ORGANOSILICIUM MATERIALS USED IN BIOMEDICAL DEVICES | |
| EP1685182B1 (en) | Silanes and silicic acid polycondensates with branched chain radicals containing urethane, acid amide and/or carboxylic acid ester groups | |
| EP0254950A2 (en) | (Meth-)acrylic esters | |
| EP0261520B1 (en) | (methyl)-acrylic-acid esters of siloxanes containing tricyclodecane groups | |
| DE2642835B2 (en) | Oxysilane compounds, processes for their preparation and their use | |
| US4742177A (en) | Methacrylic acid ester | |
| DE3219237C2 (en) | Process for the preparation of bis-allyl carbonates of dihydric alcohols | |
| EP2103622A1 (en) | Silanes and polysiloxanes | |
| DE2948301A1 (en) | METHOD FOR PRODUCING RADICAL CHAIN POLYMERIZABLE, MONOMERIC, UNSATURATED ORGANOSILICONESTER | |
| DE1593867B (en) | Process for the production of 2,2 dimethyl 2 sila 1,4 dioxane excretion from 1250448 | |
| DE3856074T2 (en) | Optically active allyl alcohol and method of making leucotriene-B4 using it | |
| DE1593867C (en) | Process for the production of 2,2 dimethyl 2 sila 1,4 dioxane excretion from 1250448 | |
| DE2263819B2 (en) | Process for the preparation of a-alkoxy w-siloxanols | |
| DE69023720T2 (en) | Fluorinated organosilicon compounds and process for their preparation. | |
| DE1595543C3 (en) | ||
| DE1248046B (en) | Process for the preparation of acyloxyorganodisiloxanes | |
| US3121106A (en) | Preparation of halogen substituted phosphoric acid esters | |
| DE102010061816A1 (en) | Process for the preparation of carbamatoorganosilanes | |
| Senchenya et al. | Silicon-containing esters of α-cyanoacrylic acid: synthesis and properties | |
| DE2120711C3 (en) | Siyl vinyl ether | |
| DE68910774T2 (en) | Cyclopentanheptenecarboxylic acid derivatives and process for their preparation. | |
| DE1593867A1 (en) | Process for the preparation of methyl derivatives of 2-sila-1,4-dioxane | |
| DE929189C (en) | Process for the production of spirocyclic esters of silicic acid | |
| Pryde et al. | Azelaaldehydic acid ester‐acetal derivatives as plasticizers for poly (vinyl chloride) | |
| DE102007047866A1 (en) | Production of acyloxy-functional organosiloxane compounds for use e.g. in production of non-stick layers or contact lenses, involves reacting the corresponding halo-organosiloxane with an acyloxysilane |