US2853527A - Production of trialkylboranes - Google Patents
Production of trialkylboranes Download PDFInfo
- Publication number
- US2853527A US2853527A US675517A US67551757A US2853527A US 2853527 A US2853527 A US 2853527A US 675517 A US675517 A US 675517A US 67551757 A US67551757 A US 67551757A US 2853527 A US2853527 A US 2853527A
- Authority
- US
- United States
- Prior art keywords
- alkyl radicals
- carbon atoms
- boric oxide
- trialkylboranes
- aluminum
- 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
- 229910011255 B2O3 Inorganic materials 0.000 claims description 11
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 11
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 229910000085 borane Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 3
- 150000002367 halogens Chemical group 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- -1 aluminum compound Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- WXRGABKACDFXMG-UHFFFAOYSA-N trimethylborane Chemical compound CB(C)C WXRGABKACDFXMG-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000463 material Substances 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
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052796 boron Inorganic materials 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
- RBHJBMIOOPYDBQ-UHFFFAOYSA-N carbon dioxide;propan-2-one Chemical compound O=C=O.CC(C)=O RBHJBMIOOPYDBQ-UHFFFAOYSA-N 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
- 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
- OFDZMBIASJPNKS-UHFFFAOYSA-L methylaluminum(2+);diiodide Chemical compound C[Al](I)I OFDZMBIASJPNKS-UHFFFAOYSA-L 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 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 trialkylboranes of the type RR'R"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.
- such trialkylboranes 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 boric oxide (B 0 and a compound of the class RAlXX' wherein R is an alkyl radical containing from'l 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 or chlorine.
- RAlXX 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.
- X and X when alkyl, can be the same as R or, if desired, R, X and X can even all be different.
- the relative proportions of bon'c oxide 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 boric oxide is within the range from about 0.75 to 12.
- the amount of RAlXX' employed can be from one-fourth to four times that stoichiometrically required to convert the boron in the boric oxide to a trialkylborane.
- the reaction between the boric oxide and RAlXX is generally carried out at a temperature within the range from about 50 C. to 200 C., although somewhat higher and somewhat lower reaction temperatures can also be used.
- the desired product can be separated from the reaction mixture using conventionalmeans, particularly by precise fractionation of the reaction mixture.
- Example I 5 grams of dry boric oxide was placed in a tube having a capacity of about 50 ml. fitted with a stopcock. The tube was cooled to 196 C. by immersion in a liquid nitrogen bath and was evacuated. 2 cc. of aluminum trimethyl was condensed into the cooled tube. The stopcock was closed and the tube was allowed to warm to room temperature. Following this, the tube was gently heated for four hours at C. During this time, the aluminum trimethyl was refluxed off of the both: oxide. At the end of this time, the reaction tube was immersed in a Dry Ice-acetone bath at 78 C. An infrared spectrum of the material that was volatile at -78 C. was identical with the spectrum of pure trimethyl borane.
- the yield of the trimethylborane was Example II Dry boric oxide, 5 grams, was placed in a 35 cc. three necked flask fitted with a pressurized addition funnel, reflux condenser, and stopper. Aluminum methyl iodide, (composed of approximately equal amounts by weight of CH AlI and (CH AlI), 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. After evacuation the liquid nitrogen bath was removed from the flask and the aluminum methyl iodide was added to and refluxed from the boric oxide for four hours. At the end of this time the trap was immersed in a bath cooled to 78 C. The infrared spectrum of the material volatile at 78 C. was identical to one of pure trimethylborane. The yield of trimethylborane was 50 mg.
- a method for the production of a trialkyl borane which comprises reacting boric oxide and a compound of the class RADQC at a temperature within the range from about 50 C. to about 200 C., R being an alkyl radical containing from- 1 to 4 carbon atoms, X being selected from the group consisting of halogen atoms and alkyl radicals containing from 1 to 4 carbon atoms, 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 RAlXX' to the number of boron atoms introduced into the reaction zone in the boric oxide being within the range from 0.75 to 12.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Description
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. 675,517
4 Claims. (Cl. 260-6065) This invention relates to a method for the production of trialkylboranes of the type RR'R"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 trialkylboranes, 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 boric oxide (B 0 and a compound of the class RAlXX' wherein R is an alkyl radical containing from'l 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 or chlorine. Thus, RAlXX 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. X and X, when alkyl, can be the same as R or, if desired, R, X and X can even all be different. In carrying out the reaction, the relative proportions of bon'c oxide 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 boric oxide is within the range from about 0.75 to 12. In other words, the amount of RAlXX' employed can be from one-fourth to four times that stoichiometrically required to convert the boron in the boric oxide to a trialkylborane. The reaction between the boric oxide and RAlXX is generally carried out at a temperature within the range from about 50 C. to 200 C., although somewhat higher and somewhat lower reaction temperatures can also be used. After the reaction has been carried out to produce the trialkyl borane,
the desired product can be separated from the reaction mixture using conventionalmeans, particularly by precise fractionation of the reaction mixture.
The following examples illustrate various embodiments which fall within the scope of this invention.
4. The method of claim 1 aluminum,
Patented Sept. 23, 1958 Example I 5 grams of dry boric oxide was placed in a tube having a capacity of about 50 ml. fitted with a stopcock. The tube was cooled to 196 C. by immersion in a liquid nitrogen bath and was evacuated. 2 cc. of aluminum trimethyl was condensed into the cooled tube. The stopcock was closed and the tube was allowed to warm to room temperature. Following this, the tube was gently heated for four hours at C. During this time, the aluminum trimethyl was refluxed off of the both: oxide. At the end of this time, the reaction tube was immersed in a Dry Ice-acetone bath at 78 C. An infrared spectrum of the material that was volatile at -78 C. was identical with the spectrum of pure trimethyl borane. The yield of the trimethylborane was Example II Dry boric oxide, 5 grams, was placed in a 35 cc. three necked flask fitted with a pressurized addition funnel, reflux condenser, and stopper. Aluminum methyl iodide, (composed of approximately equal amounts by weight of CH AlI and (CH AlI), 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. After evacuation the liquid nitrogen bath was removed from the flask and the aluminum methyl iodide was added to and refluxed from the boric oxide for four hours. At the end of this time the trap was immersed in a bath cooled to 78 C. The infrared spectrum of the material volatile at 78 C. was identical to one of pure trimethylborane. The yield of trimethylborane was 50 mg.
What is claimed is:
1. A method for the production of a trialkyl borane which comprises reacting boric oxide and a compound of the class RADQC at a temperature within the range from about 50 C. to about 200 C., R being an alkyl radical containing from- 1 to 4 carbon atoms, X being selected from the group consisting of halogen atoms and alkyl radicals containing from 1 to 4 carbon atoms, 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 RAlXX' to the number of boron atoms introduced into the reaction zone in the boric oxide being within the range from 0.75 to 12.
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. wherein RAlXX is trimethyl No references cited.
Claims (1)
1. A METHOD FOR THE PRODUCTION OF A TRIALKYL BORANE WHICH COMPRISES REACTING BORIC OXIDE AND A COMPOUND OF THE CLASS RAIXX'' AT A TEMPERATURE WITHIN THE RANGE FROM ABOUT 50*C. TO ABOUT 200*C., R BEING AN ALKYL RADICAL CONTAINING FROM 1 TO 4 CARBON ATOMS X BEING SELECTED FROM THE GROUP CONSISTING OF HALOGEN ATOMS AND ALKYL RADICALS CONTIANING FROM 1 TO 4 CARBON ATOMS, 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 OD ALKYL RADICALS INTRODUCED INTO THE REACTION ZONE ON THE RAIXX'' TO THE NUMBER OF THE BORON ATOMS INTRODUCED INTO THE REACTION ZONE IN THE BORIC OXIDE BEING WITHIN THE RANGE FROM 0.75 TO 12.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US675517A US2853527A (en) | 1957-07-29 | 1957-07-29 | Production of trialkylboranes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US675517A US2853527A (en) | 1957-07-29 | 1957-07-29 | Production of trialkylboranes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2853527A true US2853527A (en) | 1958-09-23 |
Family
ID=24710841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US675517A Expired - Lifetime US2853527A (en) | 1957-07-29 | 1957-07-29 | Production of trialkylboranes |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2853527A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2934566A (en) * | 1958-04-07 | 1960-04-26 | Afn Inc | Preparation of trialkyls of boron |
| US2951093A (en) * | 1957-08-30 | 1960-08-30 | Ici Ltd | Manufacture of trialkyl boranes |
| US3014074A (en) * | 1958-07-19 | 1961-12-19 | Kali Chemie Ag | Process of preparing boron trialkyl compounds |
| US3042723A (en) * | 1959-09-26 | 1962-07-03 | Kali Chemie Ag | Preparation of boron alkyls |
-
1957
- 1957-07-29 US US675517A patent/US2853527A/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| None * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2951093A (en) * | 1957-08-30 | 1960-08-30 | Ici Ltd | Manufacture of trialkyl boranes |
| US2934566A (en) * | 1958-04-07 | 1960-04-26 | Afn Inc | Preparation of trialkyls of boron |
| US3014074A (en) * | 1958-07-19 | 1961-12-19 | Kali Chemie Ag | Process of preparing boron trialkyl compounds |
| US3042723A (en) * | 1959-09-26 | 1962-07-03 | Kali Chemie Ag | Preparation of boron alkyls |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4960916A (en) | Organometallic antimony compounds useful in chemical vapor deposition processes | |
| Brown et al. | Organoboranes. II. The Preparation and Properties of Alkyldiboranes Containing Bulky Alkyl Substituents | |
| US2853527A (en) | Production of trialkylboranes | |
| US2853526A (en) | Production of trialkylboranes | |
| GB857882A (en) | Compounds containing boron and silicon | |
| US2951871A (en) | Polyfluoroalkyl borates | |
| GB870425A (en) | Improvements in and relating to organic phosphorus compounds | |
| US2907785A (en) | Organic compounds of silicon and phosphorus and their preparation | |
| US2927124A (en) | Preparation of trimethoxyboroxine | |
| US3154561A (en) | Organic sulfide derivatives of decaborane | |
| US2939885A (en) | Production of trialkylboranes | |
| US3188345A (en) | B-halo phosphine borines | |
| US3060212A (en) | Dicyclomatic manganese coordinated with tridentate ether | |
| Bradley et al. | 979. Structural chemistry of the alkoxides. Part III. Secondary alkoxides of silicon, titanium, and zirconium | |
| US2954402A (en) | Method of producing substituted borazoles | |
| US3222121A (en) | Preparation of sodium borohydrides | |
| US3296321A (en) | Cyclic acetylenic hydrocarbon preparation | |
| US3036111A (en) | Acetylenic boron compounds and method for making the same | |
| US2990423A (en) | Hydrocarbylaminohydrocarbyl borate/diborane adducts and their preparation | |
| US2938926A (en) | Preparation of alkyldiboranes | |
| US3205240A (en) | Epoxy esters of boron acids | |
| US3167594A (en) | Process for the production of cyclopropane hydrocarbons | |
| US2867499A (en) | Conversion of sodium tetrachloroaluminate to sodium aluminum hydride | |
| US3268580A (en) | Difluoro dialkyl phosphoranes and method of preparation of difluoro hydrocarbon phosphoranes with tetrafluorohydrazine | |
| US3497540A (en) | Hydroxy-substituted silicon-containing carboranes and neocarboranes |