US2853526A - Production of trialkylboranes - Google Patents
Production of trialkylboranes Download PDFInfo
- Publication number
- US2853526A US2853526A US675515A US67551557A US2853526A US 2853526 A US2853526 A US 2853526A US 675515 A US675515 A US 675515A US 67551557 A US67551557 A US 67551557A US 2853526 A US2853526 A US 2853526A
- Authority
- US
- United States
- Prior art keywords
- alkyl radicals
- trialkylboroxine
- reaction
- trialkylboranes
- production
- 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 - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 150000002367 halogens Chemical group 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- RSYJUCYSXLRFCX-UHFFFAOYSA-N butyl(dimethyl)borane Chemical compound CCCCB(C)C RSYJUCYSXLRFCX-UHFFFAOYSA-N 0.000 description 6
- 229910052796 boron Inorganic materials 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- DQEOZNPKBKCSPK-UHFFFAOYSA-N 2,4,6-tributyl-1,3,5,2,4,6-trioxatriborinane Chemical compound CCCCB1OB(CCCC)OB(CCCC)O1 DQEOZNPKBKCSPK-UHFFFAOYSA-N 0.000 description 4
- -1 aluminum compound Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical class B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 229910000085 borane Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- OFDZMBIASJPNKS-UHFFFAOYSA-L methylaluminum(2+);diiodide Chemical compound C[Al](I)I OFDZMBIASJPNKS-UHFFFAOYSA-L 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- CGGWHUZJDXLSTD-UHFFFAOYSA-M dimethylalumanylium;iodide Chemical compound C[Al](C)I CGGWHUZJDXLSTD-UHFFFAOYSA-M 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C07F5/027—Organoboranes and organoborohydrides
Definitions
- This invention relates to a method for the production of trialkyl boranes of the type RRR"B wherein R, R and R are lower alkyl radicals, particularly those containing from 1 to 4 carbon atoms.
- R, R and R are lower alkyl radicals, particularly those containing from 1 to 4 carbon atoms.
- R, R and R are lower alkyl radicals, particularly those containing from 1 to 4 carbon atoms.
- such trialkyl boranes in the form of amine addition products, are useful additives to diesel fuels and the like for the purpose of increasing their cetane number.
- such trialkylboranes are useful for the purpose described in Klein, Nadeau, Schoen and Bliss application Serial No. 614,768, filed October 8, 1956.
- the trialkylboranes are produced by reacting a trialkylboroxine (11 E 0 and a compound of the class RAlXX.
- R and R are alkyl radicals containing from 1 to 4 carbon atoms
- X and X are alkyl radicals containing from 1 to 4 carbon atoms or are halogen atoms, particularly iodine, bromine and chlorine.
- R'AlXX' can be a trialkyl aluminum compound, such as aluminum trimethyl or aluminum triethyl, or it can be an alkyl aluminum halide, such as methyl aluminum di-iodide or dimethyl aluminum monoiodide.
- the relative proportions of trialkylboroxine and RAlXX' can be varied widely.
- the ratio of the number of alkyl radicals introduced into the reaction zone in the RAlXX to the number of boron atoms introduced into the reaction zone in the trialkylboroxine is within the range from 0.5 to 8.
- the amount of R'AlXX' employed can be from one-fourth to four times that stoichiometrically required to convert the boron in the trialkylboroxine to a trialkylborane.
- the reaction between the trialkylboroxine and R'AIXX' is generally carried out at a temperature within the range from about 0 C. to 150 C., although somewhat higher and somewhat lower reaction temperatures can also be used.
- the desired product can be separated from the reaction mixture using conventional means, particularly by precise fractionation of the reaction mixture.
- Example I 3 cc. of tributylboroxine was placed in a tube having a capacity of about 50 ml. fitted with a stopcock. The
- Example 11 Aluminum methyl iodide (composed of approximately equal amounts by weight of CH AlI and (CH AlI), 5 cc. was placed in a 35 cc., S-necked flask fitted with a pressurized funnel, reflux condenser and stopper. Tributylboroxine, 5 cc., was placed in the addition funnel. The top of the reflux condenser was connected to a vacuum source through a trap immersed in liquid nitrogen. The flask was then immersed in liquid nitrogen and evacuated. The liquid nitrogen bath was then removed from the flask and the flask was permitted to warm up to room temperature.
- Tributylboroxine 5 cc.
- the tributylboroxine was added dropwise to the aluminum methyl iodide and an exceed ingly violent reaction took place, occasionally accompanied by incandescence. After the conclusion of the reaction, the flask was warmed for ten minutes by immersion in a beaker of boiling water.
- the material that volatilized was collected in a trap cooled to 196 C., this material was shown to be butyl dimethylborane by vapor density, boron alalysis and boron and nitrogen analyses of its pyridine adduct. The yield was 90 percent, based upon the methyl content of the methyl aluminum iodide.
- the theoretical analysis calculated for butyl dimethylborane is 11.1 weight percent of boron and the calculated molecular weight is 98.
- the butyl dimethylborane obtained in this reaction contained 11.5, 11.4 weight percent boron and had a molecular weight of 100, 102.
- the butyl dimethylborane isolated as the reaction product weighed 2.0 grams and had a vapor pressure between mm. and mm. of mercury at room temperature.
- a method for the production of a trialkylborane which comprises reacting a trialkylboroxine of the formula R B O and a compound of the class RAlXX' at a temperature within the range from about 0 C. to about C., R and R being alkyl radicals containing from 1 to 4 carbon atoms, X and X being selected from the group consisting of halogen atoms and alkyl radicals containing from 1 to 4 carbon atoms, and the ratio of the number of alkyl radicals introduced into the reaction zone in the R'AlXX' to the number of boron atoms introduced into the reaction zone in the trialkylboroxine being within the range from 0.5 to 8.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Description
. same kind.
United States Patent PRODUCTION OF TRIALKYLBORANES John C. Perrine, Jr., Pasadena, Calif., assignor to Olin Mathieson Chemical Corporation, a corporation of Virginia No Drawing. Application July 29, 1957 Serial No. 675,515
4 Claims. (Cl. 260-6065) This invention relates to a method for the production of trialkyl boranes of the type RRR"B wherein R, R and R are lower alkyl radicals, particularly those containing from 1 to 4 carbon atoms. As is described in U. S. Patent No. 2,266,776, to Leum, such trialkyl boranes, in the form of amine addition products, are useful additives to diesel fuels and the like for the purpose of increasing their cetane number. In addition, such trialkylboranes are useful for the purpose described in Klein, Nadeau, Schoen and Bliss application Serial No. 614,768, filed October 8, 1956.
In accordance with the present invention, the trialkylboranes are produced by reacting a trialkylboroxine (11 E 0 and a compound of the class RAlXX. R and R are alkyl radicals containing from 1 to 4 carbon atoms, and X and X are alkyl radicals containing from 1 to 4 carbon atoms or are halogen atoms, particularly iodine, bromine and chlorine. Thus, R'AlXX' can be a trialkyl aluminum compound, such as aluminum trimethyl or aluminum triethyl, or it can be an alkyl aluminum halide, such as methyl aluminum di-iodide or dimethyl aluminum monoiodide. If desired, by appropriate choice of the reactants, it is possible in accordance with the method of the present invention to prepare mixed trialkylboranes or, on the other hand, it is possible to prepare trialkylboranes wherein each alkyl radical is of the In carrying out the reaction, the relative proportions of trialkylboroxine and RAlXX' can be varied widely. Preferably, however, the ratio of the number of alkyl radicals introduced into the reaction zone in the RAlXX to the number of boron atoms introduced into the reaction zone in the trialkylboroxine is within the range from 0.5 to 8. In other words, the amount of R'AlXX' employed can be from one-fourth to four times that stoichiometrically required to convert the boron in the trialkylboroxine to a trialkylborane. The reaction between the trialkylboroxine and R'AIXX' is generally carried out at a temperature within the range from about 0 C. to 150 C., although somewhat higher and somewhat lower reaction temperatures can also be used. After the reaction has been carried out to produce the trialkylboroxine, the desired product can be separated from the reaction mixture using conventional means, particularly by precise fractionation of the reaction mixture.
The following examples illustrate various embodiments which fall within the scope of this invention.
Example I 3 cc. of tributylboroxine was placed in a tube having a capacity of about 50 ml. fitted with a stopcock. The
ICC
tube was immersed in a liquid nitrogen bath whereby it was cooled to -196 C., and was then evacuated. 1.5 grams of aluminum trimethyl was condensed into the tube containing the tributylboroxine. As the tube was allowed to warm to room temperature, a very violent reaction took place. The volatile material present in the tube was collected in a trap cooled to l96 C. An infrared spectrum of this volatile material showed that the product was butyl dimethylborane. The butyl dimethylborane obtained weighed 2.75 grams.
Example 11 Aluminum methyl iodide (composed of approximately equal amounts by weight of CH AlI and (CH AlI), 5 cc. was placed in a 35 cc., S-necked flask fitted with a pressurized funnel, reflux condenser and stopper. Tributylboroxine, 5 cc., was placed in the addition funnel. The top of the reflux condenser was connected to a vacuum source through a trap immersed in liquid nitrogen. The flask was then immersed in liquid nitrogen and evacuated. The liquid nitrogen bath was then removed from the flask and the flask was permitted to warm up to room temperature. The tributylboroxine was added dropwise to the aluminum methyl iodide and an exceed ingly violent reaction took place, occasionally accompanied by incandescence. After the conclusion of the reaction, the flask was warmed for ten minutes by immersion in a beaker of boiling water.
The material that volatilized was collected in a trap cooled to 196 C., this material was shown to be butyl dimethylborane by vapor density, boron alalysis and boron and nitrogen analyses of its pyridine adduct. The yield was 90 percent, based upon the methyl content of the methyl aluminum iodide. The theoretical analysis calculated for butyl dimethylborane is 11.1 weight percent of boron and the calculated molecular weight is 98. The butyl dimethylborane obtained in this reaction contained 11.5, 11.4 weight percent boron and had a molecular weight of 100, 102. The butyl dimethylborane isolated as the reaction product weighed 2.0 grams and had a vapor pressure between mm. and mm. of mercury at room temperature.
What is claimed is:
l. A method for the production of a trialkylborane which comprises reacting a trialkylboroxine of the formula R B O and a compound of the class RAlXX' at a temperature within the range from about 0 C. to about C., R and R being alkyl radicals containing from 1 to 4 carbon atoms, X and X being selected from the group consisting of halogen atoms and alkyl radicals containing from 1 to 4 carbon atoms, and the ratio of the number of alkyl radicals introduced into the reaction zone in the R'AlXX' to the number of boron atoms introduced into the reaction zone in the trialkylboroxine being within the range from 0.5 to 8.
2. The method of claim 1 wherein X and X are alkyl radicals.
3. The method of claim 1 wherein X and X are iodine.
4. The method of claim 1 wherein RAlXX is trimethylaluminum.
No references cited.
Claims (1)
1. A METHOD FOR THE PRODUCTION OF A TRIALKYLBORANE WHICH COMPRISES REACTING A TRIALKYLBOROXINE OF THE FORMULA R3B3O3 AND A COMPOUND OF THE CLASS R''AIXX'' AT A TEMPERATURE WITHIN THE RANGE FROM ABOUT 0*. TO ABOUT 150*C., R AND R'' BEING ALKYL RADICALS CONTAINING FROM 1 TO 4 CARBON X AND X'' BEING SELECTED FROM THE GROUP CONSISTING OF HALOGEN ATOMS AND ALKYL RADICALS CONTAINING FRO 1 TO 4 CARBON ATOMS, AND THE RATIO OF THE NUMBER OF ALKYL RADICALS INTRODUCED INTO THE REACTION ZONE IN THE R''AIXX'' TO THE NUMBER OF BORON ATOMS INTRODUCED INTO THE REACTION ZONE IN THE TRIALKYLBOROXINE BEING WITHIN THE RANGE FROM 0.5 TO 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US675515A US2853526A (en) | 1957-07-29 | 1957-07-29 | Production of trialkylboranes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US675515A US2853526A (en) | 1957-07-29 | 1957-07-29 | Production of trialkylboranes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2853526A true US2853526A (en) | 1958-09-23 |
Family
ID=24710832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US675515A Expired - Lifetime US2853526A (en) | 1957-07-29 | 1957-07-29 | Production of trialkylboranes |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2853526A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3014074A (en) * | 1958-07-19 | 1961-12-19 | Kali Chemie Ag | Process of preparing boron trialkyl compounds |
| US3023248A (en) * | 1959-04-06 | 1962-02-27 | Ethyl Corp | Production of organoboranes |
| US3049407A (en) * | 1957-10-03 | 1962-08-14 | Studiengesellschaft Kohle Mbh | Process for the production of boron alkyls and of highly active aluminium oxide |
| US3087953A (en) * | 1958-01-22 | 1963-04-30 | Studiengesellschaft Kohle Mbh | Process for the exchange of hydrocarbon groups between aluminium and boron hydrocarbon compounds |
| US5411925A (en) * | 1993-02-12 | 1995-05-02 | Phillips Petroleum Company | Organo-aluminoxy product and use |
-
1957
- 1957-07-29 US US675515A patent/US2853526A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3049407A (en) * | 1957-10-03 | 1962-08-14 | Studiengesellschaft Kohle Mbh | Process for the production of boron alkyls and of highly active aluminium oxide |
| US3087953A (en) * | 1958-01-22 | 1963-04-30 | Studiengesellschaft Kohle Mbh | Process for the exchange of hydrocarbon groups between aluminium and boron hydrocarbon compounds |
| US3014074A (en) * | 1958-07-19 | 1961-12-19 | Kali Chemie Ag | Process of preparing boron trialkyl compounds |
| US3023248A (en) * | 1959-04-06 | 1962-02-27 | Ethyl Corp | Production of organoboranes |
| US5411925A (en) * | 1993-02-12 | 1995-05-02 | Phillips Petroleum Company | Organo-aluminoxy product and use |
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