DE1121613B - Process for the preparation of esters of alkyl boric acids - Google Patents
Process for the preparation of esters of alkyl boric acidsInfo
- Publication number
- DE1121613B DE1121613B DEF31573A DEF0031573A DE1121613B DE 1121613 B DE1121613 B DE 1121613B DE F31573 A DEF31573 A DE F31573A DE F0031573 A DEF0031573 A DE F0031573A DE 1121613 B DE1121613 B DE 1121613B
- Authority
- DE
- Germany
- Prior art keywords
- esters
- preparation
- boric acids
- alkyl boric
- alkyl
- 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
- -1 alkyl boric acids Chemical class 0.000 title claims description 11
- 150000002148 esters Chemical class 0.000 title claims description 8
- 235000010338 boric acid Nutrition 0.000 title claims description 6
- 238000000034 method Methods 0.000 title description 6
- 238000002360 preparation method Methods 0.000 title description 3
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- BMMZDTNPYHSDMO-UHFFFAOYSA-N oxolane-2-carboxylic acid;trifluoroborane Chemical compound FB(F)F.OC(=O)C1CCCO1 BMMZDTNPYHSDMO-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- NOXNXVPLDITALF-UHFFFAOYSA-N butoxyboronic acid Chemical compound CCCCOB(O)O NOXNXVPLDITALF-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- CHNLPLHJUPMEOI-UHFFFAOYSA-N oxolane;trifluoroborane Chemical compound FB(F)F.C1CCOC1 CHNLPLHJUPMEOI-UHFFFAOYSA-N 0.000 description 1
- JMVWCCOXRGFPJZ-UHFFFAOYSA-N propoxyboronic acid Chemical compound CCCOB(O)O JMVWCCOXRGFPJZ-UHFFFAOYSA-N 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/025—Boronic and borinic acid compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Description
Verfahren zur Herstellung von Estern der Alkylborsäuren Zusatz zum Patent 1 094 747 Gegenstand des Patentes 1 094 747 ist ein Verfahren zur Herstellung von Estern der Alkylborsäuren, das dadurch gekennzeichnet ist, daß Halogenborsäureester mit Boranaten und Olefinen umgesetzt und gegebenenfalls die erhaltenen Ester mit Alkoholen umgeestert werden.Process for the preparation of esters of alkyl boric acids addition to Patent 1,094,747 The subject of patent 1,094,747 is a method of manufacture of esters of alkyl boric acids, which is characterized in that haloboric acid esters reacted with boranates and olefins and optionally the esters obtained with Alcohols are interesterified.
Gegenstand der Erfindung ist eine weitere Ausbildung dieses Verfahrens zur Herstellung von Estern der Alkylborsäuren, das darin besteht, daß Borsäureester mit Boranaten, Olefinen und organischen Anlagerungsverbindungen der Borhalogenide umgesetzt werden. The subject of the invention is a further development of this method for the preparation of esters of alkyl boric acids, which consists in that boric acid esters with boranates, olefins and organic addition compounds of boron halides implemented.
Es wurde gefunden, daß sich die im Hauptpatent beschriebene Herstellung der Alkylborsäureester noch einfacher gestalten läßt, wenn an Stelle der Halogenborsäureester Borsäureester und organische Anlagerungsverbindungen der Borhalogenide eingesetzt werden. Ein erheblicher Fortschritt des neuen Verfahrens liegt darin, daß sich Halogenborsäureester aus Borsäureestern und Borhalogeniden nur in etwa 80"/figer Ausbeute gewinnen lassen, während sich z. B. das Bortrifluorid-Tetrahydrofuranat in fast quantitativer Ausbeute herstellen läßt. Ein weiterer Vorteil liegt darin, daß die destillative Aufarbeitung der Endprodukte leichter vonstatten geht. It was found that the production described in the main patent the alkyl boric acid ester can be made even simpler if instead of the haloboric acid ester Boric acid esters and organic addition compounds of boron halides are used will. A significant advance of the new process is that haloboric acid esters from boric acid esters and boron halides can only be obtained in about 80 "/ figer yield, while z. B. the boron trifluoride tetrahydrofuranate in almost quantitative yield can be produced. Another advantage is that the work-up by distillation that makes the end product easier.
Das erfindungsgemäße Verfahren läßt sich für den Fall des Bortrifluorid-Tetrahydrofuran-Adduktes beispielsweise durch folgende Gleichungen beschreiben : 2B (OR) 3 + 4BF3-THF + 3 NaBH4 + 12C3H6 o6 (C3H7) 2BOR + 3 NaBF4 + 4THF 8B (OR) 3+4BF3. THF + 3NaBH, + 12CgHs + 12 C3H7B (OR) 2 + 3 NaBF4 + 4 THF wobei R einen organischen Rest bedeutet. The process according to the invention can be applied to the case of the boron trifluoride-tetrahydrofuran adduct For example, describe it by the following equations: 2B (OR) 3 + 4BF3-THF + 3 NaBH4 + 12C3H6 o6 (C3H7) 2BOR + 3 NaBF4 + 4THF 8B (OR) 3 + 4BF3. THF + 3NaBH, + 12CgHs + 12 C3H7B (OR) 2 + 3 NaBF4 + 4 THF where R is an organic radical.
Die Umsetzung geschieht bevorzugt bei erhöhten Temperaturen. Die Verwendung von Lösungs-bzw. The reaction is preferably carried out at elevated temperatures. the Use of solution or.
Suspensionsmitteln, z. B. Kohlenwasserstoffen oder Athem, wie Diäthylenglykoldimethyläther oder Tetrahydrofuran, ist von Vorteil.Suspending agents, e.g. B. hydrocarbons or breath, such as diethylene glycol dimethyl ether or tetrahydrofuran, is beneficial.
Beispiel 2B (OC4H9) 3 + 4BF3-THF+ 3NaBH4 + 12C3H6 - (CgHBOQH, + 3 NaBF4 H 4THF In 2,4 I trockenem Tetrahydrofuran werden 137 g (3,6 Mole) feingepulvertes Natriumboranat suspendiert. Unter Rühren und gleichzeitigem Einleiten von Propylen werden 460 g (2 Mol) Borsäure-n-butylester und 560 g (4 Mol) Bortrifluorid-Tetrahydrofuranat gleichmäßig eingetropft, wobei die Reaktionstemperatur 40 bis 60°C beträgt. Nach beendigtem Zutropfen kocht man 4 Stunden unter Propylendurchleiten am Rückfluß, kühlt ab, filtriert, wäscht den Filtrationsrückstand mit trockenem Tetrahydrofuran aus und destilliert das Tetrahydrofuran bei Normaldruck ab. Example 2B (OC4H9) 3 + 4BF3-THF + 3NaBH4 + 12C3H6 - (CgHBOQH, + 3 NaBF4 H 4THF In 2.4 l of dry tetrahydrofuran, 137 g (3.6 moles) are finely powdered Suspended sodium boranate. With stirring and simultaneous introduction of propylene 460 g (2 mol) of boric acid n-butyl ester and 560 g (4 mol) of boron trifluoride tetrahydrofuranate are obtained added dropwise uniformly, the reaction temperature being 40 to 60 ° C. To When the dropwise addition is complete, the mixture is refluxed for 4 hours while propylene is passed through, cools down, filtered, and the filtration residue was washed with dry tetrahydrofuran and the tetrahydrofuran is distilled off at normal pressure.
Den Rückstand fraktioniert man im Vakuum. Man erhält in 84°/Oiger Ausbeute Dipropylborsäure-n-butylester neben Propylborsäuredi-n-butylester.The residue is fractionated in vacuo. One receives in 84 ° / Oiger Yield of dipropylboric acid n-butyl ester in addition to propylboric acid di-n-butyl ester.
Claims (1)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF29686A DE1094747B (en) | 1959-10-23 | 1959-10-23 | Process for the preparation of esters of alkyl boric acids |
| DEF31573A DE1121613B (en) | 1959-10-23 | 1960-07-02 | Process for the preparation of esters of alkyl boric acids |
| GB3626461A GB929656A (en) | 1959-10-23 | 1960-10-21 | Production of esters of alkylboronic acids and dialkylborinic acids |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF29686A DE1094747B (en) | 1959-10-23 | 1959-10-23 | Process for the preparation of esters of alkyl boric acids |
| DEF31573A DE1121613B (en) | 1959-10-23 | 1960-07-02 | Process for the preparation of esters of alkyl boric acids |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1121613B true DE1121613B (en) | 1962-01-11 |
Family
ID=25974462
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF29686A Pending DE1094747B (en) | 1959-10-23 | 1959-10-23 | Process for the preparation of esters of alkyl boric acids |
| DEF31573A Pending DE1121613B (en) | 1959-10-23 | 1960-07-02 | Process for the preparation of esters of alkyl boric acids |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEF29686A Pending DE1094747B (en) | 1959-10-23 | 1959-10-23 | Process for the preparation of esters of alkyl boric acids |
Country Status (2)
| Country | Link |
|---|---|
| DE (2) | DE1094747B (en) |
| GB (1) | GB929656A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4795821A (en) * | 1986-08-29 | 1989-01-03 | Aldrich-Boranes, Inc. | Optically active borinic esters and ketones |
| CN112746289B (en) * | 2021-01-21 | 2021-11-09 | 合肥工业大学 | Synthesis method of alkyl borate compound |
-
1959
- 1959-10-23 DE DEF29686A patent/DE1094747B/en active Pending
-
1960
- 1960-07-02 DE DEF31573A patent/DE1121613B/en active Pending
- 1960-10-21 GB GB3626461A patent/GB929656A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE1094747B (en) | 1960-12-15 |
| GB929656A (en) | 1963-06-26 |
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