JP2017105848A - 第iiia族金属のトリアルキル化合物の調製方法 - Google Patents
第iiia族金属のトリアルキル化合物の調製方法 Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 22
- 239000002184 metal Substances 0.000 title claims abstract description 22
- 150000002739 metals Chemical class 0.000 title abstract 2
- 238000004519 manufacturing process Methods 0.000 title description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 15
- 239000002585 base Substances 0.000 claims abstract description 15
- 229910001508 alkali metal halide Inorganic materials 0.000 claims abstract description 5
- 150000008045 alkali metal halides Chemical class 0.000 claims abstract description 5
- 230000000737 periodic effect Effects 0.000 claims abstract description 5
- 239000011541 reaction mixture Substances 0.000 claims description 49
- 238000002360 preparation method Methods 0.000 claims description 27
- 150000002736 metal compounds Chemical class 0.000 claims description 23
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000004064 recycling Methods 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 53
- 238000006243 chemical reaction Methods 0.000 abstract description 46
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 45
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 42
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 37
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 34
- 239000000047 product Substances 0.000 description 30
- 239000000203 mixture Substances 0.000 description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- 235000011164 potassium chloride Nutrition 0.000 description 18
- 239000001103 potassium chloride Substances 0.000 description 18
- 239000011780 sodium chloride Substances 0.000 description 17
- -1 alkyl gallium compounds Chemical class 0.000 description 16
- 239000003153 chemical reaction reagent Substances 0.000 description 16
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 description 14
- 230000002152 alkylating effect Effects 0.000 description 13
- 239000007858 starting material Substances 0.000 description 13
- 229910052733 gallium Inorganic materials 0.000 description 12
- 238000002955 isolation Methods 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 9
- 238000009835 boiling Methods 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 9
- 239000007788 liquid Substances 0.000 description 9
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- HYZXMVILOKSUKA-UHFFFAOYSA-K chloro(dimethyl)alumane;dichloro(methyl)alumane Chemical compound C[Al](C)Cl.C[Al](Cl)Cl HYZXMVILOKSUKA-UHFFFAOYSA-K 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000029936 alkylation Effects 0.000 description 5
- 238000005804 alkylation reaction Methods 0.000 description 5
- 125000002524 organometallic group Chemical group 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 4
- OWQWEJKPOUNPPG-UHFFFAOYSA-M chloro(dimethyl)gallane Chemical compound C[Ga](C)Cl OWQWEJKPOUNPPG-UHFFFAOYSA-M 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- CMAOLVNGLTWICC-UHFFFAOYSA-N 2-fluoro-5-methylbenzonitrile Chemical compound CC1=CC=C(F)C(C#N)=C1 CMAOLVNGLTWICC-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 230000001035 methylating effect Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- 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 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 2
- OTRPZROOJRIMKW-UHFFFAOYSA-N triethylindigane Chemical compound CC[In](CC)CC OTRPZROOJRIMKW-UHFFFAOYSA-N 0.000 description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- KAXRWMOLNJZCEW-UHFFFAOYSA-N 2-amino-4-(2-aminophenyl)-4-oxobutanoic acid;sulfuric acid Chemical compound OS(O)(=O)=O.OC(=O)C(N)CC(=O)C1=CC=CC=C1N KAXRWMOLNJZCEW-UHFFFAOYSA-N 0.000 description 1
- 229910016467 AlCl 4 Inorganic materials 0.000 description 1
- 229910021617 Indium monochloride Inorganic materials 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 229910001515 alkali metal fluoride Inorganic materials 0.000 description 1
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- FOJZPLNOZUNMJO-UHFFFAOYSA-M chloro(dimethyl)indigane Chemical compound [Cl-].C[In+]C FOJZPLNOZUNMJO-UHFFFAOYSA-M 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- SPIUPAOJDZNUJH-UHFFFAOYSA-N diethylmercury Chemical compound CC[Hg]CC SPIUPAOJDZNUJH-UHFFFAOYSA-N 0.000 description 1
- JGHYBJVUQGTEEB-UHFFFAOYSA-M dimethylalumanylium;chloride Chemical compound C[Al](C)Cl JGHYBJVUQGTEEB-UHFFFAOYSA-M 0.000 description 1
- ATZBPOVXVPIOMR-UHFFFAOYSA-N dimethylmercury Chemical compound C[Hg]C ATZBPOVXVPIOMR-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 1
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JOTBHEPHROWQDJ-UHFFFAOYSA-N methylgallium Chemical compound [Ga]C JOTBHEPHROWQDJ-UHFFFAOYSA-N 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 238000010517 secondary reaction Methods 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 1
- JHUXFIPODALNAN-UHFFFAOYSA-N tris(2-methylpropyl)gallane Chemical compound CC(C)C[Ga](CC(C)C)CC(C)C JHUXFIPODALNAN-UHFFFAOYSA-N 0.000 description 1
- 238000010518 undesired secondary reaction Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
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- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
- C23C16/18—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material from metallo-organic compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/301—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
Description
R3M
(式中、Mは、元素周期表(PTE)の第IIIA族金属、好ましくはガリウム(Ga)またはインジウム(In)であり、かつRは、C1〜C5−アルキル基、好ましくはメチルまたはエチルである)
を有する。
R3M
(式中、
M=元素周期表(PTE)の第IIIA族金属
R=C1〜C5−アルキル、好ましくはメチルまたはエチル)
で示されるトリアルキル金属化合物の調製方法を提供する。本方法は、以下の工程、すなわち、
a)補助ベースとしての少なくとも1種のアルカリ金属ハロゲン化物の存在下で金属三塩化物(MCl3)とアルキルアルミニウムセスキクロリド(R3Al2Cl3)とを反応させる工程と、
b)反応混合物を120℃超の温度に加熱して、分離器を介して反応混合物からトリアルキル金属化合物(R3M)を分離するとともに、MClxRy型(式中、x、y=1または2、かつx+y=3)の部分アルキル化生成物を反応混合物に再循環する工程と、
c)反応混合物を165℃〜350℃の範囲内の温度に加熱して、残存するトリアルキル金属化合物(R3M)および部分アルキル化生成物(MClxRy)を分離する工程と、
を含む。
d)工程c)で得られたトリアルキル金属化合物(R3M)および部分アルキル化生成物MClxRyを反応混合物で再使用する工程、
をさらに含む。
1=トリアルキル金属化合物R3M
2=分離器
3=部分アルキル化金属化合物MClxRy
4=反応混合物(T>120℃)
GaCl3+Me3Al2Cl3+2Na/KCl→Me3Ga+2Na/KAlCl4 (1)
GaCl3+Me3Al2Cl3+2Na/KCl→Me2GaCl+Na/KMeAlCl3+Na/KAlCl4 (2)
Me2GaCl+Na/KMeAlCl3→Me3Ga+Na/KAlCl4 (3)
生成物および合成に使用されるセスキクロリドは、自燃性である。したがって、作業はすべて、空気および湿気を厳密に排除して保護ガス(アルゴン、窒素)下で行われる。
トリメチルガリウム(TMG)の調製
200.0g(1.14mol)のGaCl3(高純度、MCP Group,Tilly,BE)、92.9g(1.59mol、1.4当量)の無水NaCl(Merck、水含有率<5ppm)、および50.8g(0.68mol、0.6当量)の無水KCl(Merck、水含有率<5ppm)を、撹拌機と滴下漏斗と分離器としての70℃に維持された充填塔とそのほかにさらなる出口とを備えた500ml四口フラスコ内の不活性ガス(アルゴン、純度6.0)下に配置する。撹拌しながら、反応混合物の温度が130℃を超えないように、233.5g(1.14mol、1当量)のメチルアルミニウムセスキクロリド(Me3Al2Cl3、Chemtura Organometallics GmbH,Bergkamen,DE)を添加する。GaCl3対Me3Al2Cl3の当量比は、1:1である。
(TMG、再使用による)
183.1g(1.04mol)のGaCl3、92.9g(1.59mol)の無水NaCl、50.8g(0.68mol)の無水KCl、さらには40.4g(0.3mol)のMe2GaClおよび5.5g(0.05mol)のMe3Ga(実施例1から単離された混合物)を、撹拌機と滴下漏斗と分離器としての70℃に維持された充填塔とそのほかにさらなる出口とを備えた500ml四口フラスコ内の不活性ガス(アルゴン、純度6.0)下に配置する。
(TMG、当量比1:3)
45.0g(0.26mol)のGaCl3、62.7g(1.07mol、4.2当量)の無水NaCl、および34.3g(0.46mol、1.8当量)の無水KClを、撹拌機と滴下漏斗と分離器としての70℃に維持された充填塔とを備えた500ml四口フラスコ内のアルゴン下に配置する。
(トリエチルガリウムTEGの調製)
200.0g(1.14mol)のGaCl3、92.9g(1.59mol、1.4当量)の無水NaCl(水含有率<5ppm)、および50.8g(0.7mol、0.6当量)の無水KCl(水含有率<5ppm)を、撹拌機と滴下漏斗と分離器としての160℃に維持された充填塔とを備えた500ml四口フラスコ内の不活性ガス(アルゴン)下に配置する。
(トリエチルガリウムの調製(TEG、減圧)
68.9g(0.39mol)のGaCl3、の32.0g(0.55mol、1.4当量)無水NaCl、および17.5g(0.23mol、0.6当量)の無水KClを、撹拌機と滴下漏斗と130℃に維持された分離器とを備えた500ml四口フラスコ内のアルゴン下に配置する。
(TMG、当量比1:1.5)
170g(0.97mol)のGaCl3、118.5g(2.03mol、2.1当量)の無水NaCl、および64.9g(0.87mol、0.9当量)の無水KClを、撹拌機と滴下漏斗と分離器としての70℃に維持された充填塔とを備えた500ml四口フラスコ内のアルゴン下に配置する。
(TMG、分離器を使用せず)
実験条件は、実施例6と同一であるが、実験は、分離器を使用せずに行われる。
(独国特許第4005726号明細書の実施例4に係るTMG)
撹拌機と熱電対と滴下漏斗とを備えた500ml四口フラスコにGaCl3(50.0g、0.28mol)を仕込み、滴下漏斗を介してメチルアルミニウムセスキクロリド(58.3g、0.28mol、1当量)を滴下する。反応混合物を室温に冷却した後、フラスコをグローブボックスに移動して、無水NaCl(23.2g、0.40mol、1.4当量)および無水KCl(12.7g、0.17mol、0、6当量)を添加する。滴下漏斗をコールドトラップが装着されたクライゼンヘッドと交換する。この装置をグローブボックスから取り出し、一定した撹拌下で反応混合物を350℃に徐々に加熱する。100〜120℃の温度で、反応混合物が液体になり、155〜160℃で、透明液体が留去し始めて氷冷コールドトラップ中に捕集される。室温で部分的に固体の全量36.9gの捕集された生成物は、21.3%のMe3Gaと78.7%のMe2GaClとを含有するMe3GaとMe2GaClとの混合物としてNMRにより同定される。
トリメチルインジウム(TMI)の調製
グローブボックス内で、撹拌機と熱電対と滴下漏斗とコールドトラップ付き分離器とを備えた250ml四口フラスコに、InCl3(10.0g、45.2mmol)、無水NaCl(3.67g、63.3mmol、1.40当量)、および無水KCl(2.02g、27.1mmol、0.6当量)を仕込み、そして滴下漏斗にメチルアルミニウムセスキクロリド(9.29g、45.2mmol、1.0当量)を仕込む。装置をグローブボックスから取り出して、メチルアルミニウムセスキクロリドを塩混合物に添加する。次いで、80℃に設定された分離器温度を用いて、一定した撹拌下で反応混合物を150℃に徐々に加熱する。反応混合物が完全に液体であるとき、コールドトラップを液体窒素で冷却し、装置に真空(10−3mbar)を適用することにより、トリメチルインジウムをコールドトラップ中に昇華させる。すべてのトリメチルインジウムが反応フラスコから昇華したとき、分離器を介する生成物の単離を停止し、新しいコールドトラップを反応フラスコに直接装着し、温度を250℃まで上昇させることにより、反応混合物中に残存するジメチルインジウムクロリドを昇華させる。
Claims (1)
- 以下の工程、すなわち、
a)補助ベースとしての少なくとも1種のアルカリ金属ハロゲン化物の存在下で金属三塩化物(MCl3)とアルキルアルミニウムセスキクロリド(R3Al2Cl3)とを反応させる工程と、
b)反応混合物を120℃超の温度に加熱して、分離器を介して反応混合物からトリアルキル金属化合物(R3M)を分離するとともに、MClxRy型(式中、x、y=1または2、かつx+y=3)の部分アルキル化生成物を反応混合物に再循環する工程と、
c)反応混合物を165℃〜350℃の範囲内の温度に加熱して、残存するトリアルキル金属化合物(R3M)および部分アルキル化生成物(MClxRy)を反応混合物から分離する工程と、
を含む、一般式
R3M
(式中、
M=元素周期表(PTE)の第IIIA族金属
R=C1〜C5−アルキル、好ましくはメチルまたはエチル)
で示されるトリアルキル金属化合物の調製方法。
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