GB2305916A - Dialkylindium halide preparation - Google Patents
Dialkylindium halide preparation Download PDFInfo
- Publication number
- GB2305916A GB2305916A GB9619132A GB9619132A GB2305916A GB 2305916 A GB2305916 A GB 2305916A GB 9619132 A GB9619132 A GB 9619132A GB 9619132 A GB9619132 A GB 9619132A GB 2305916 A GB2305916 A GB 2305916A
- Authority
- GB
- United Kingdom
- Prior art keywords
- reaction
- hours
- solvent
- dialkylindium
- trialkylindium
- 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.)
- Granted
Links
- 150000004820 halides Chemical class 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 229910052738 indium Inorganic materials 0.000 claims abstract description 7
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 238000010992 reflux Methods 0.000 claims abstract description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 27
- 238000000034 method Methods 0.000 claims description 22
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical group Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 12
- 229960004132 diethyl ether Drugs 0.000 claims description 6
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical group C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 claims description 4
- 101100341029 Caenorhabditis elegans inx-3 gene Proteins 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 125000001033 ether group Chemical group 0.000 claims 1
- QAKYGMVUNQSJFH-UHFFFAOYSA-N tripropylindigane Chemical group CCC[In](CCC)CCC QAKYGMVUNQSJFH-UHFFFAOYSA-N 0.000 claims 1
- 150000002367 halogens Chemical class 0.000 abstract description 2
- FOJZPLNOZUNMJO-UHFFFAOYSA-M chloro(dimethyl)indigane Chemical compound [Cl-].C[In+]C FOJZPLNOZUNMJO-UHFFFAOYSA-M 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- -1 indium halide Chemical class 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- BHKKSKOHRFHHIN-MRVPVSSYSA-N 1-[[2-[(1R)-1-aminoethyl]-4-chlorophenyl]methyl]-2-sulfanylidene-5H-pyrrolo[3,2-d]pyrimidin-4-one Chemical compound N[C@H](C)C1=C(CN2C(NC(C3=C2C=CN3)=O)=S)C=CC(=C1)Cl BHKKSKOHRFHHIN-MRVPVSSYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011369 resultant mixture Substances 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000007787 solid 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
Dialkylindium halides of formula R* subscript minus *InX, R being an alkyl group and X being a halogen, are prepared by reacting a trialkylindium (R* superscript dot; dot above *In) with an indium trihalide (InX* superscript dot; dot above *), suitably in a solvent, eg ethyl acetate, under reflux for an extended period of time.
Description
TITLE: Preparation of dialkylindium halides.
DESCRIPTION
This invention concerns the preparation of dialkylindium halides.
Dimethylindium chloride is a useful precursor for deposition of indium containing films by chemical vapour deposition.
The preparation of dimethylindium chloride is described in J. Organometal Chem. 8 (1967) 427-434 in which dried indium trichloride is reacted with methyllithium in ether. The reaction can be summarised as follows:
InC13 + 2MeLi ether)Me2InCl + 2 LiCl Methyllithuim is an expensive material and because it is soluble in ether only up to about 5% by weight, it is only obtainable in very dilute solutions.
Consequently it is difficult to scale up preparation of dimethylindium chloride using the above method due to the size of plant required.
An object of this invention is to provide an alternative preparation for dialkylindium halides.
It has now been found that a dialkylindium halide can be prepared by reaction of trialkylindium and indium trihalide.
Accordingly the present invention provides a method of preparing a dialkylindium halide of the formula R2InX, wherein R represents an alkyl group, especially a methyl or a propyl group, and X represents a halogen, by reacting a trialkylindium (R3In) with an indium trihalide (InX3).
The reaction is preferably carried out in a solvent and preferably under reflux.
The reaction involved is believed to be in accordance with the following equation:
To increase yields of the dialkylindium halide the reaction needs to be carried out over an extended period of time. Preferably the solvent is ethyl acetate and the reaction is continued for a period of 3 to 7 hours, especially 5 hours. Alternatively, the solvent may be an ether1 such as for example, diethylether, in which case useful yields of the dialkylindium halide may be obtained after 50 hours but preferably the reaction is continued for at least 100 hours, especially for at least 160 hours. The shorter the reaction time, the more monoalkylindium dihalide is produced, although it may be possible to separate the mono- and dialkylcomponents from the reaction mixture.
After completion of the reaction, the solvent may be removed by any suitable means to leave the dialkyl indium halide product. The solvent may be removed by vacuum distillation or by distillation at atmospheric pressure.
The method of the invention is particularly suitable for preparing dimethylindium chloride from trimethylindium and indium trichloride but other halide derivatives may be prepared as well as, for example, dipropylindium halides.
This invention will now be further described by means of the following Examples.
Example 1
Dimethylindium chloride was prepared as follows: 11.5g of trimethylindium were dissolved in 100ml of diethylether (Merck degassed). To the resultant solution were added 7.8g anhydrous indium trichloride and the mixture was stirred and ref fluxed at about 500C for over 160 hours.
After ref fluxing the diethylether was pumped off at room temperature for several hours to leave a white crystalline material identified as dimethylindium chloride by analysis. The following Table shows a comparison between the calculated carbon, hydrogen and chlorine weight percentages for dimethylindium chloride and those found for the reaction product:
TABLE
C H Cl
Calculated 13.3 3.3 19.6
Found 13.1 3.0 19.2
The yield of dimethylindium chloride was found to be over 90%.
EXAMPLE 2
Dimethylindium chloride was prepared as follows:
58g of anhydrous indium trichloride were added to 200 ml of ethyl acetate and the mixture was stirred.
85.5g of trimethylindium were dissolved in 150ml of diethyl ether and this solution slowly added to the mixture of indium trichloride in ethyl acetate over a period of 1.45 hours. The resultant solution was then stirred for a further 2.5 hour. The resultant mixture was filtered and the diethyl ether was then distilled off, followed by the ethyl acetate. The resultant solid was analysed for C,H and Cl content.
TABLE
C H Cl
Calculated 13.3 3.3 19.6
Found 13.2 3.2 19.4
The melting point was checked and found to be 215.50C which corresponds closely to that of DMIn Cl of 2160C.
The yield was found to be 95%.
Claims (19)
1. A method of preparing a dialkylindium halide of the formula R2InX, wherein R represents an alkyl group and X represents a halogen, by reacting a trialkylindium (R3In) with an indium trihalide (InX3).
2. A method as claimed in claim 1, wherein R is a methyl group.
3. A method as claimed in claim 1, wherein R is an propyl group.
4. A method as claimed in claim 1, 2 or 3 wherein the reaction is carried out in a solvent.
5. A method as claimed in any one of claims 1 to 4, wherein the reaction is carried out under reflux.
6. A method as claimed in claim 4 or 5 wherein the solvent is ethyl acetate.
7. A method as claimed in claim 6, wherein the reaction is carried over a period of 3-7 hours.
8. A method as claimed in claim 7, wherein the reaction is continued for 5 hours.
9. A method as claimed in claim 4 or 5, wherein the solvent is an ether.
10. A method as claimed in claim 9, wherein the ether is diethylether.
11. A method as claimed in claim 9 or 10, wherein the reaction is carried out over a period of at least 50 hours.
12. A method as claimed in claim 11, wherein the reaction is continued for at least 100 hours.
13. A method as claimed in claim 12, wherein the reaction is continued for at least 160 hours.
14. A method as claimed in any one of claims 4 to 13, wherein the solvent is removed by distillation.
15. A method as claimed in claim 14, wherein the solvent is removed by vacuum distillation.
16. A method as claimed in any one of the preceding claims wherein the trialkylindium is trimethylindium and the indium trihalide is indium trichloride.
17. A method as claimed in any one of claims 1 to 15 wherein the trialkylindium is tripropylindium.
18. A method as claimed in claim 1 and substantially as hereinbefore described, with reference to any one of the foregoing Examples.
19. A dialkylindium halide of the formula R2InX wherein R represents an alkyl group and X represents a halogen, whenever prepared according to a method as claimed in any one of the preceding claims.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GBGB9518667.2A GB9518667D0 (en) | 1995-09-13 | 1995-09-13 | Preparation of dialkylindium halides |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB9619132D0 GB9619132D0 (en) | 1996-10-23 |
| GB2305916A true GB2305916A (en) | 1997-04-23 |
| GB2305916B GB2305916B (en) | 1999-01-20 |
Family
ID=10780620
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GBGB9518667.2A Pending GB9518667D0 (en) | 1995-09-13 | 1995-09-13 | Preparation of dialkylindium halides |
| GB9619132A Expired - Fee Related GB2305916B (en) | 1995-09-13 | 1996-09-13 | Preparation of dialkylindium halides |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GBGB9518667.2A Pending GB9518667D0 (en) | 1995-09-13 | 1995-09-13 | Preparation of dialkylindium halides |
Country Status (1)
| Country | Link |
|---|---|
| GB (2) | GB9518667D0 (en) |
-
1995
- 1995-09-13 GB GBGB9518667.2A patent/GB9518667D0/en active Pending
-
1996
- 1996-09-13 GB GB9619132A patent/GB2305916B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| GB9619132D0 (en) | 1996-10-23 |
| GB9518667D0 (en) | 1995-11-15 |
| GB2305916B (en) | 1999-01-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 20120913 |