CA2040240A1 - Process for the preparation of methanolic methyltri-n-alkylphosphonium iodide solution - Google Patents
Process for the preparation of methanolic methyltri-n-alkylphosphonium iodide solutionInfo
- Publication number
- CA2040240A1 CA2040240A1 CA002040240A CA2040240A CA2040240A1 CA 2040240 A1 CA2040240 A1 CA 2040240A1 CA 002040240 A CA002040240 A CA 002040240A CA 2040240 A CA2040240 A CA 2040240A CA 2040240 A1 CA2040240 A1 CA 2040240A1
- Authority
- CA
- Canada
- Prior art keywords
- methyltri
- alkylphosphonium
- iodide
- preparation
- methanolic
- 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.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 13
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003085 diluting agent Substances 0.000 claims abstract description 12
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000007717 exclusion Effects 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 4
- 238000005810 carbonylation reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 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
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 230000006315 carbonylation Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- -1 phosphonium halides Chemical class 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 0.000 description 2
- RMZAYIKUYWXQPB-UHFFFAOYSA-N trioctylphosphane Chemical compound CCCCCCCCP(CCCCCCCC)CCCCCCCC RMZAYIKUYWXQPB-UHFFFAOYSA-N 0.000 description 2
- KCTAHLRCZMOTKM-UHFFFAOYSA-N tripropylphosphane Chemical compound CCCP(CCC)CCC KCTAHLRCZMOTKM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- MCWXGJITAZMZEV-UHFFFAOYSA-N dimethoate Chemical compound CNC(=O)CSP(=S)(OC)OC MCWXGJITAZMZEV-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- FVQGXIOJWSAQHM-UHFFFAOYSA-M methyl(trioctyl)phosphanium;iodide Chemical compound [I-].CCCCCCCC[P+](C)(CCCCCCCC)CCCCCCCC FVQGXIOJWSAQHM-UHFFFAOYSA-M 0.000 description 1
- VBLKCVJGAOUJAL-UHFFFAOYSA-M methyl(tripropyl)phosphanium;iodide Chemical compound [I-].CCC[P+](C)(CCC)CCC VBLKCVJGAOUJAL-UHFFFAOYSA-M 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000003003 phosphines Chemical group 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- RLZMYANQLOCZOB-UHFFFAOYSA-M tributyl(methyl)phosphanium;iodide Chemical compound [I-].CCCC[P+](C)(CCCC)CCCC RLZMYANQLOCZOB-UHFFFAOYSA-M 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5407—Acyclic saturated phosphonium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Process for the preparation of methanolic methyltri-n-alkylphosphonium iodide solution Abstract of the disclosure A process for the preparation of methanolic methyltri-n-alkylphosphonium iodide solution having 3 to 8 carbon atoms in the carbon chain and prepared from tri-n-alkyl-phosphine and methyl iodide in a diluent is described, in which methanol is used as the diluent.
Description
&
The lnvention relates -to a process for the preparation of methanolic methyltri-n-alkylphosphonium iodide solut.i.on having 3 to 8 carbon atoms in the carbon chain and prepared from ~ri-n-alkylphosphine and methyl iodide in a diluent.
Quaternary phosphonium salts are effective promoters in carbonylation reactions for preparing acetic acid and acetic anhydride where noble metal compounds, in par-ticular rhodium compounds, are used as the catalyst.
Suitable preparation methods are described in DE-A-2,450,965.
~ecently, in particular the rhodiumcarbonyl complexes [CH3P(C4Hg) 3 ~ Rh(CO)I4 or [CH3P(C4Hg) 3 ] Rh ( CO )2I2 are described for effective catalyst systems (EP-B-0,240,703).
The quaternary phosphonium halides axe prepared according to the reaction scheme R~P + Hal-R' ~ [R3~-R'~Hal~
When methyl iodide is reacted with tertiary phosphines, a very vigorous reaction occurs, making necessary the use of diluents, such as ether or benzene (HOUBEN-WEYL:
"Methoden der Organischen Chemie" [Methods of Organic Chemistry], 1963, volume 12.l, page 79).
In industry, hexane is nowadays used as the diluent. The dis~dvantage of all previously utilized diluents is that the quaternary phosphonium halide precipitates as a salt and has to be separated off from the diluent before further use as a promoter in carbonylation reactions.
Surprisingly, it has now been found that the reaction of tri-n alkylphosphine having 3 to 8 carbon atoms in the carbon chain with methyl iodide takes place in a homo-geneous phase if methanol is used as the diluent. The formation of the desired phosphonium sal~s by this method takes place quantitatively, relative to the component 20~0240 used in less than an equivalent amount.
The process of the invention can furthermore preferably and alternatively comprise a) carrying out the reaction with the exclusion of air, b) using tri-n-alkylphosphine and methyl iodide in a ` molar ratio of 1 to (1.1 to 0.95), .:, c) adjusting the molar ratio of methyltri-n-alkyl-phosphonium iodide to methanol to 1 to ~1 to 20), in ~` particular to 1 to (4 to 10).
:, The process of the invention makes it unnecessary to completely separate off a foreign diluent and to redis-`~ solve the methyltri-n-alkylphosphonium iodide in the reaction mixture of the carbonylation; furthermore, the carbonylation products are not contaminated with a foreign diluent and the purification or disposal of the foxeign diluent which is contaminated after multiple use is omitted.
; Example 1 A mixture of 168 g (1.05 mol) of tri-n-propylphosphine : 20 and 320 g of methanol is initially introduced into a 1 1 multi-neck flask, equipped with stirrer, internal thermo-meter, reflux condenser, dropping funnel and nitrogen introduction line, which has been rendered inert with nitrogen. 150 g (1.06 mol) of methyl iodide are added dropwise to this mixture at room temperature over a period of 2 hours with vigorous stirring. After the dropwise addition is completed and the exothermic reac-tion has subsided, the reaction mixture is kept under reflux conditions for another hour.
The 31p NMR spectrum of the clear, colorless solution no longer showed any signal of the starting compound tri-n-propylphosphine (-33 ppm). 99% of the 31p NMR signal intensity for methyltripropylphosphonium iodide was found 20~0240 at +31 ppm.
- Example 2 202 g (1 mol) of tributylphosphine and 160 g (5 mol) of methanol are initially introduced into a O.S l multi-neck flask, equipped with stirrer, internal thermometer, dropping funnel, reflux condenser and nitrogen introduc-tion line, which has been rendered inert. Under an inert gas atmosphere, the mixture is heated to 60C, and lS7 g (1.1 mol) of methyl iodide are added dropwise over a i. 10 period of 40 minutes. The enthalpy of the reaction which is liberated keeps the mixture boiling without any additional heat input. After the addition of methyl iodide, the clear, colorless reaction mixture is kept at 65C for another 45 minutes.
Analysis of the 31p NMR spectrum of the product showed that the tributylphosphine had been converted quantita-tively to methyltributylphosphonium iodide (+32 ppm).
Example 3 As described in Example 2, 70 g (0.5 mol) of methyl iodide are added dropwise to 190 g (0.52 mol) of tri-n-octylphosphine in 275 g of methanol. The reaction is allowed to continue at 65C for another 2 hours.
As expected, in addition to traces of oxide and residual unconverted tri-n-octylphosphine (3.5%; -32.5 ppm), only methyltrioctylphosphonium iodide (+31 ppm) was found in the 31p NMR spectrum of the product.
The lnvention relates -to a process for the preparation of methanolic methyltri-n-alkylphosphonium iodide solut.i.on having 3 to 8 carbon atoms in the carbon chain and prepared from ~ri-n-alkylphosphine and methyl iodide in a diluent.
Quaternary phosphonium salts are effective promoters in carbonylation reactions for preparing acetic acid and acetic anhydride where noble metal compounds, in par-ticular rhodium compounds, are used as the catalyst.
Suitable preparation methods are described in DE-A-2,450,965.
~ecently, in particular the rhodiumcarbonyl complexes [CH3P(C4Hg) 3 ~ Rh(CO)I4 or [CH3P(C4Hg) 3 ] Rh ( CO )2I2 are described for effective catalyst systems (EP-B-0,240,703).
The quaternary phosphonium halides axe prepared according to the reaction scheme R~P + Hal-R' ~ [R3~-R'~Hal~
When methyl iodide is reacted with tertiary phosphines, a very vigorous reaction occurs, making necessary the use of diluents, such as ether or benzene (HOUBEN-WEYL:
"Methoden der Organischen Chemie" [Methods of Organic Chemistry], 1963, volume 12.l, page 79).
In industry, hexane is nowadays used as the diluent. The dis~dvantage of all previously utilized diluents is that the quaternary phosphonium halide precipitates as a salt and has to be separated off from the diluent before further use as a promoter in carbonylation reactions.
Surprisingly, it has now been found that the reaction of tri-n alkylphosphine having 3 to 8 carbon atoms in the carbon chain with methyl iodide takes place in a homo-geneous phase if methanol is used as the diluent. The formation of the desired phosphonium sal~s by this method takes place quantitatively, relative to the component 20~0240 used in less than an equivalent amount.
The process of the invention can furthermore preferably and alternatively comprise a) carrying out the reaction with the exclusion of air, b) using tri-n-alkylphosphine and methyl iodide in a ` molar ratio of 1 to (1.1 to 0.95), .:, c) adjusting the molar ratio of methyltri-n-alkyl-phosphonium iodide to methanol to 1 to ~1 to 20), in ~` particular to 1 to (4 to 10).
:, The process of the invention makes it unnecessary to completely separate off a foreign diluent and to redis-`~ solve the methyltri-n-alkylphosphonium iodide in the reaction mixture of the carbonylation; furthermore, the carbonylation products are not contaminated with a foreign diluent and the purification or disposal of the foxeign diluent which is contaminated after multiple use is omitted.
; Example 1 A mixture of 168 g (1.05 mol) of tri-n-propylphosphine : 20 and 320 g of methanol is initially introduced into a 1 1 multi-neck flask, equipped with stirrer, internal thermo-meter, reflux condenser, dropping funnel and nitrogen introduction line, which has been rendered inert with nitrogen. 150 g (1.06 mol) of methyl iodide are added dropwise to this mixture at room temperature over a period of 2 hours with vigorous stirring. After the dropwise addition is completed and the exothermic reac-tion has subsided, the reaction mixture is kept under reflux conditions for another hour.
The 31p NMR spectrum of the clear, colorless solution no longer showed any signal of the starting compound tri-n-propylphosphine (-33 ppm). 99% of the 31p NMR signal intensity for methyltripropylphosphonium iodide was found 20~0240 at +31 ppm.
- Example 2 202 g (1 mol) of tributylphosphine and 160 g (5 mol) of methanol are initially introduced into a O.S l multi-neck flask, equipped with stirrer, internal thermometer, dropping funnel, reflux condenser and nitrogen introduc-tion line, which has been rendered inert. Under an inert gas atmosphere, the mixture is heated to 60C, and lS7 g (1.1 mol) of methyl iodide are added dropwise over a i. 10 period of 40 minutes. The enthalpy of the reaction which is liberated keeps the mixture boiling without any additional heat input. After the addition of methyl iodide, the clear, colorless reaction mixture is kept at 65C for another 45 minutes.
Analysis of the 31p NMR spectrum of the product showed that the tributylphosphine had been converted quantita-tively to methyltributylphosphonium iodide (+32 ppm).
Example 3 As described in Example 2, 70 g (0.5 mol) of methyl iodide are added dropwise to 190 g (0.52 mol) of tri-n-octylphosphine in 275 g of methanol. The reaction is allowed to continue at 65C for another 2 hours.
As expected, in addition to traces of oxide and residual unconverted tri-n-octylphosphine (3.5%; -32.5 ppm), only methyltrioctylphosphonium iodide (+31 ppm) was found in the 31p NMR spectrum of the product.
Claims (5)
1. A process for the preparation of a methanolic solu-tion of methyltri-n-alkylphosphonium iodide having 3 to 8 carbon atoms in the carbon chain, which comprises reacting tri-n-alkylphosphine with methyl iodide in methanol as the diluent.
2. The process as claimed in claim 1, wherein the reaction is carried out with the exclusion of air.
3. The process as claimed in claim 1, wherein tri-n-alkylphosphine is reacted with methyl iodide in a molar ratio of 1 to (1.1 to 0.95).
4. The process as claimed in claim 1, wherein the molar ratio of methyltri-n-alkylphosphonium iodide to methanol is adjusted to 1 to (1 to 20).
5. The process as claimed in claim 4, wherein the molar ratio is 1 to (4 to 10).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE4014073A DE4014073A1 (en) | 1990-05-02 | 1990-05-02 | METHOD FOR PRODUCING METHANOLIC METHYL-TRI-N-ALKYL-PHOSPHONIUM IODIDE SOLUTION |
| DEP4014073.3 | 1990-05-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2040240A1 true CA2040240A1 (en) | 1991-11-03 |
Family
ID=6405572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002040240A Abandoned CA2040240A1 (en) | 1990-05-02 | 1991-04-11 | Process for the preparation of methanolic methyltri-n-alkylphosphonium iodide solution |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0455982A1 (en) |
| JP (1) | JPH04225991A (en) |
| AU (1) | AU632937B2 (en) |
| CA (1) | CA2040240A1 (en) |
| DE (1) | DE4014073A1 (en) |
| ZA (1) | ZA913258B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8916727B2 (en) | 2011-12-16 | 2014-12-23 | Celanese International Corporation | Production of acetic acid with enhanced catalyst stability |
-
1990
- 1990-05-02 DE DE4014073A patent/DE4014073A1/en not_active Withdrawn
-
1991
- 1991-04-03 EP EP91105288A patent/EP0455982A1/en not_active Withdrawn
- 1991-04-11 CA CA002040240A patent/CA2040240A1/en not_active Abandoned
- 1991-04-26 AU AU76231/91A patent/AU632937B2/en not_active Ceased
- 1991-04-30 ZA ZA913258A patent/ZA913258B/en unknown
- 1991-05-01 JP JP3100120A patent/JPH04225991A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8916727B2 (en) | 2011-12-16 | 2014-12-23 | Celanese International Corporation | Production of acetic acid with enhanced catalyst stability |
Also Published As
| Publication number | Publication date |
|---|---|
| DE4014073A1 (en) | 1991-11-07 |
| ZA913258B (en) | 1992-01-29 |
| JPH04225991A (en) | 1992-08-14 |
| EP0455982A1 (en) | 1991-11-13 |
| AU7623191A (en) | 1991-11-07 |
| AU632937B2 (en) | 1993-01-14 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |