US3641081A - Process for preparing dialkylzinc compounds from alkylbromide - Google Patents
Process for preparing dialkylzinc compounds from alkylbromide Download PDFInfo
- Publication number
- US3641081A US3641081A US792852*A US3641081DA US3641081A US 3641081 A US3641081 A US 3641081A US 3641081D A US3641081D A US 3641081DA US 3641081 A US3641081 A US 3641081A
- Authority
- US
- United States
- Prior art keywords
- zinc
- alloy
- reaction
- sodium
- alkylbromide
- 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
- 150000001875 compounds Chemical class 0.000 title abstract description 16
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 150000001347 alkyl bromides Chemical class 0.000 title description 16
- 239000011701 zinc Substances 0.000 abstract description 52
- 239000011734 sodium Substances 0.000 abstract description 30
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 28
- 229910052708 sodium Inorganic materials 0.000 abstract description 23
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 22
- 229910052725 zinc Inorganic materials 0.000 abstract description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 17
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052700 potassium Inorganic materials 0.000 abstract description 16
- 239000011591 potassium Substances 0.000 abstract description 16
- 229910052744 lithium Inorganic materials 0.000 abstract description 15
- 229910001297 Zn alloy Inorganic materials 0.000 description 38
- 238000006243 chemical reaction Methods 0.000 description 31
- 238000000034 method Methods 0.000 description 21
- 229910045601 alloy Inorganic materials 0.000 description 19
- 239000000956 alloy Substances 0.000 description 19
- 229960003975 potassium Drugs 0.000 description 15
- 235000007686 potassium Nutrition 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 229910000528 Na alloy Inorganic materials 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- 238000010992 reflux Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 7
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 6
- 229910000799 K alloy Inorganic materials 0.000 description 6
- 229910000733 Li alloy Inorganic materials 0.000 description 5
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- -1 zinc halide Chemical class 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 150000001351 alkyl iodides Chemical class 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- HEPBQSXQJMTVFI-UHFFFAOYSA-N zinc;butane Chemical compound [Zn+2].CCC[CH2-].CCC[CH2-] HEPBQSXQJMTVFI-UHFFFAOYSA-N 0.000 description 3
- YXZFFTJAHVMMLF-UHFFFAOYSA-N 1-bromo-3-methylbutane Chemical compound CC(C)CCBr YXZFFTJAHVMMLF-UHFFFAOYSA-N 0.000 description 2
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 description 2
- KEVMYFLMMDUPJE-UHFFFAOYSA-N 2,7-dimethyloctane Chemical compound CC(C)CCCCC(C)C KEVMYFLMMDUPJE-UHFFFAOYSA-N 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 2
- DMAYBPBPEUFIHJ-UHFFFAOYSA-N 4-bromobut-1-ene Chemical compound BrCCC=C DMAYBPBPEUFIHJ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 101150065749 Churc1 gene Proteins 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 102100038239 Protein Churchill Human genes 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 description 2
- 230000004927 fusion Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000001989 lithium alloy Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229940102396 methyl bromide Drugs 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- SRYDABIEWPHLGE-UHFFFAOYSA-N C=CC(C)[Zn]C(C=C)C Chemical compound C=CC(C)[Zn]C(C=C)C SRYDABIEWPHLGE-UHFFFAOYSA-N 0.000 description 1
- QWBLLZKMJQONQN-UHFFFAOYSA-N CC(C)CC[Zn]CCC(C)C Chemical compound CC(C)CC[Zn]CCC(C)C QWBLLZKMJQONQN-UHFFFAOYSA-N 0.000 description 1
- CRIGZHQSHKIPFT-UHFFFAOYSA-N CCCCC[Zn]CCCCC Chemical compound CCCCC[Zn]CCCCC CRIGZHQSHKIPFT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 102000020897 Formins Human genes 0.000 description 1
- 108091022623 Formins Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- KSHPUQQHKKJVIO-UHFFFAOYSA-N [Na].[Zn] Chemical compound [Na].[Zn] KSHPUQQHKKJVIO-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000005267 amalgamation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZMMJGEGLRURXTF-UHFFFAOYSA-N ethidium bromide Chemical compound [Br-].C12=CC(N)=CC=C2C2=CC=C(N)C=C2[N+](CC)=C1C1=CC=CC=C1 ZMMJGEGLRURXTF-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910002058 ternary alloy Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
-
- 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
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/06—Zinc compounds
Definitions
- This invention relates to a direct process for preparing dialkylzinc compounds.
- Diorganic compounds are generally prepared by two methods.
- the first method reacts a zinc halide with a reactive organometallic, such as lithium or magnesium, in an ether solvent.
- the second method involves a direct synthesis starting from metallic zinc or zinc alloys with alkyl iodides. Mixtures of alkyl bromides and iodides have also previously been used in combination with zinccopper alloy.
- the first method is disadvantageous in that it requires two separate steps to be performed. In the first step the lithium or magnesium reagent must be formed, and in the second step the actual formation of the organozinc compound takes place.
- An additional disadvantage is the presence in the reaction of flammable solvents. The separation of the solvents from the product is not always ealiilly achieved, especially with the utilization of lower a ys.
- the second method is more attractive in that only one step is required and the use of solvents is not necessary, although recent attempts to find improved conditions have utilized solvents with'high dielectric constants, such as dimethylformamide.
- solvents with'high dielectric constants such as dimethylformamide.
- the use of solvents makes it impossible to separate solvent from the product.
- the reaction usually begins a few minutes after the starting materials have made contact with each other, especially if substantially all traces of moisture have been removed from the atmosphere and the apparatus. Heating of the reaction mixture may be necessary to begin the reaction, but if the reaction is exothermal refluxing temperature is maintained without the application of external heat. In the event that the reaction is not exothermal, external heating may be applied to maintain the reflux temperature. It has been found that a temperature in the range of 40-l80 C. is satisfactory. A temperature range of l00-l40 C. is preferred.
- the reaction is considered complete when refluxing stops.
- the flask is connected with a distilling head and the contents of the flask are distilled under reduced pressure. Distillation of the product mixture vaporizes the dialkylzinc compound which is captured as a distillation product.
- the zinc alloys which have proved themselves reliable for purposes of the invention are the lithium, potassium and sodium alloys.
- the alloys may be formed by fusing the metals together in a steel crucible under an inert atmosphere, for example, argon. The cooled melt is machined to fine particle size. Usually turnings may be used, but if the alloy is very brittle a sandlike material is obtained upon machining.
- the shot method may also be utilized to prepare the alloys on an industrial scale.
- the maximum amount of sodium which can be alloyed with zinc is one atom of sodium per twelve atoms of zinc. This corresponds with an alloy containing three wt. percent sodium, the balance being zinc.
- Table I contains data showing the yield of dialkylzinc in relation to the percentage of sodium in the alloy.
- Zinc alloyed with potassium is obtained by fusing zinc and potassium under an inert atmosphere, such as nitrogen, and machining in the usual way.
- the alloy is very reactive and should be kept in an inert atmosphere.
- the maximum amount of potassium in the zinc/potas sium alloy is approximately 5 wt. percent, which corresponds to a molar ratio of 12 moles zinc to 1 mole potassium. .
- the reaction with the alkylbromide is carried out in the same manner as with the zinc/sodium alloy. Once begun, the reaction continues spontaneously upon addition of the bromide.
- the potassium content of the alloy may be reduced without loss of activity.
- the zinc/potassium alloys are easily handled and machined to small particle size.
- the 2% potassium/zinc alloy is well suited for the direct synthesis of zinc dialkyls, although the yields in general are somewhat lower than for the zinc/ sodium alloys.
- the recommended range would be 0.5-5.0 wt. percent potassium with 1.5 to 2.0 wt. percent potassium preferred.
- a useful lithium range is 1 to wt. percent lithium in the zinc alloy, with a preferred content of approximately 2 wt. percent lithium.
- Ternary alloys may be used to provide good yields of dialkylzinc compounds.
- the amalgamation of the zinc/ sodium alloy by treating the 3% sodium/zinc alloy with HgCl in tetrahydrofuran provides approximately the same yield as using the zinc/sodium alloy without the Hgcl
- An alloy composed of 2.6% sodium, 1.1% mercury and the rest zinc was reacted with butyl'brornide and yielded 52% dibutylzinc.
- the synthesis according to the invention may be carried out with both normal and branched chain alkylbromides. Since longer chain dialkylzincs, for example, where R is greater than C have limited thermal stability, a direct synthesis involving thermal cracking of primarily formed RZnBr to give R Zn+ZnBr is not practical. At the other end of the scale, the boiling point of methyl bromide is low and requires reaction under higher pressure conditions than atmospheric pressure.
- Hg contained some 2,7-dimethyloctane (the Wurtz coupling product of iso-amylbromide) as, appeared from a gas chromatoe graphic analysis of the hydrolysis products).
- the yield of di-isoamylzinc after refractionation, B.P. 64-,689/ 2 mm.) was 5.48 g. (46% of theory).
- EXAMPLE 5 I 1 n-Bu Zn from ZnK alloy (2% K) and n-BuBr A mixture of 29.0 g. of finely divided Zn-2.0 K. alloy (0.44 g. at. Zn) and 5.0 ml. of n-BuBr was gradually warmed up (to oil bath temp, of When reaction had started -18 ml. of n-BuBr (0.22 mole n"-BuBr.in total)v was added dropwise' After a further 30 min hea'ting period 10.8 g. n-Bu Zn (55% of theory) was isolated by distillation in vacuo.
- a process for preparing dialkylzinc compounds comprising:
- an alloy of zinc having at least one metal selected from the group consisting of sodium, potassium, and lithium, the amount of metal in the alloy being about 1 to about 3 weight percent sodium, about 0.5 to about 5.0 weight percent potassium and about 1 to about 10 weight percent lithium, with the remaining percentage being zinc, with (ii) a reagent consisting essentially of alkylbromide in a molar ratio of at least 1 to 1, zinc to alkylbromide, wherein the alkyl radical is selected from the group consisting of saturated and unsaturated alkyl radicals containing from 1 to -8 carbon atoms; and
- alkylbromide is selected from the group consisting of methylbromide and ethylbromide, and the alkylbromide is re fiuxed under a pressure above that of atmospheric pressure.
- dialkylzinc is added to the reaction mixture to remove traces of moisture.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US79285269A | 1969-01-21 | 1969-01-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3641081A true US3641081A (en) | 1972-02-08 |
Family
ID=25158280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US792852*A Expired - Lifetime US3641081A (en) | 1969-01-21 | 1969-01-21 | Process for preparing dialkylzinc compounds from alkylbromide |
Country Status (6)
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4187254A (en) * | 1976-11-09 | 1980-02-05 | Societe Chimique Des Charbonnages - Cdf Chimie | Grignard reagents and processes for making them |
| US4385003A (en) * | 1981-10-30 | 1983-05-24 | Stauffer Chemical Company | Dialkylzinc composition having improved thermal stability |
| US4402880A (en) * | 1981-10-30 | 1983-09-06 | Stauffer Chemical Company | Dialkylzinc compositions having improved thermal stability |
| US4407758A (en) * | 1981-10-30 | 1983-10-04 | Stauffer Chemical Company | Dialkylzinc compositions having improved thermal stability |
| US6521771B2 (en) * | 2000-05-19 | 2003-02-18 | Goldschmidt Ag | Use of zinc treated with metal hydride in organometallic synthesis |
| CN109128064A (zh) * | 2018-09-21 | 2019-01-04 | 北京科技大学 | 一种可生物降解Zn-Na系锌合金及其制备方法 |
-
1969
- 1969-01-21 US US792852*A patent/US3641081A/en not_active Expired - Lifetime
- 1969-05-19 BE BE733267D patent/BE733267A/xx unknown
- 1969-05-20 DE DE19691925652 patent/DE1925652A1/de active Pending
- 1969-05-22 NL NL6907898A patent/NL6907898A/xx unknown
- 1969-05-28 GB GB26884/69A patent/GB1243305A/en not_active Expired
- 1969-06-20 FR FR6920828A patent/FR2028746A1/fr not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4187254A (en) * | 1976-11-09 | 1980-02-05 | Societe Chimique Des Charbonnages - Cdf Chimie | Grignard reagents and processes for making them |
| US4385003A (en) * | 1981-10-30 | 1983-05-24 | Stauffer Chemical Company | Dialkylzinc composition having improved thermal stability |
| US4402880A (en) * | 1981-10-30 | 1983-09-06 | Stauffer Chemical Company | Dialkylzinc compositions having improved thermal stability |
| US4407758A (en) * | 1981-10-30 | 1983-10-04 | Stauffer Chemical Company | Dialkylzinc compositions having improved thermal stability |
| US6521771B2 (en) * | 2000-05-19 | 2003-02-18 | Goldschmidt Ag | Use of zinc treated with metal hydride in organometallic synthesis |
| CN109128064A (zh) * | 2018-09-21 | 2019-01-04 | 北京科技大学 | 一种可生物降解Zn-Na系锌合金及其制备方法 |
| CN109128064B (zh) * | 2018-09-21 | 2020-04-28 | 北京科技大学 | 一种可生物降解Zn-Na系锌合金及其制备方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2028746A1 (US06580902-20030617-M00005.png) | 1970-10-16 |
| BE733267A (US06580902-20030617-M00005.png) | 1969-11-03 |
| NL6907898A (US06580902-20030617-M00005.png) | 1970-07-23 |
| DE1925652A1 (de) | 1970-10-01 |
| GB1243305A (en) | 1971-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| GB829574A (en) | Method for the preparation of metallo-organic compounds | |
| US3641081A (en) | Process for preparing dialkylzinc compounds from alkylbromide | |
| US2992248A (en) | Processes for preparing halo group iii-a hydrides and halo group iii-a hydrocarbons | |
| US2596690A (en) | Preparation of boron compounds | |
| US2921954A (en) | Novel vinyl borons and method of preparation | |
| US3641080A (en) | Process for preparing dialkylizinc compounds from alkylbromide and alkyliodide | |
| US3887598A (en) | Process for the manufacture of metal complexes in a pure form | |
| US2838556A (en) | Organo-aluminum compounds | |
| US3006942A (en) | Recovery of by-product aluminum and preparation of aluminum alkyls | |
| US5211887A (en) | High purity alkyllithium compounds and process of preparation | |
| US4291167A (en) | Preparation of tetramethyldisilane from 1,2-tetramethyldichlorodisilane | |
| US2927124A (en) | Preparation of trimethoxyboroxine | |
| US3052702A (en) | Preparation of organolead compounds | |
| US3155736A (en) | Method of making organolithium compounds | |
| US3047358A (en) | Preparation of boron-hydrogen compounds | |
| US2575760A (en) | Preparation of heavy metal borohydrides | |
| US3045049A (en) | Halogen containing organic derivatives of decaborane | |
| US3396012A (en) | Recovery of silicon from alloys thereof and from silicon sulfides | |
| US4960869A (en) | Uranium allylic complex | |
| US3647839A (en) | Synthesis of tetramethyllead | |
| US2942017A (en) | Organozinc sulfate and sulfonate compounds | |
| US3401189A (en) | Tetramethyl lead manufacture | |
| US3389187A (en) | Perfluoroisobutylene dimer | |
| US3927060A (en) | Method of producing diethyldifluorosilane | |
| US2951093A (en) | Manufacture of trialkyl boranes |