CA2109349A1 - Process for the preparation of chlorophenylphosphanes - Google Patents
Process for the preparation of chlorophenylphosphanesInfo
- Publication number
- CA2109349A1 CA2109349A1 CA 2109349 CA2109349A CA2109349A1 CA 2109349 A1 CA2109349 A1 CA 2109349A1 CA 2109349 CA2109349 CA 2109349 CA 2109349 A CA2109349 A CA 2109349A CA 2109349 A1 CA2109349 A1 CA 2109349A1
- Authority
- CA
- Canada
- Prior art keywords
- zone
- silicon carbide
- pcl3
- reaction
- bulk material
- 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
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 System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/52—Halophosphines
Abstract
Process for the preparation of chlorophenylphosphanes Abstract For preparation of chlorophenylphosphanes of the formula (C6H5)n PCl3-n in which n is 1 or 2, triphenylphosphane (C6H5)3P and phosphorus trichloride PCl3 are reacted at temperatures above 300°C, for which liquid triphenylphosphane and gaseous phosphorus trichloride are introduced in the given molar ratio at the top of a vertically arranged, elongated and heated reaction zone. The reaction product discharged at the foot of the reaction zone is trans-ferred to a residence zone charged with phosphorus pentachloride. Finally, the excess phosphorus trichloride is removed from the reaction product, via a subsequent fractionating zone, by heating the residence zone.
Description
2 1~3~
The present invention relates to a process for the preparation of chlorophenylphosphanes of the formula (C5Hs)n PC13 n ~ in which n is 1 or 2, by reaction of triphenylphosphane i. 5 (C6H5)3P and phosphorus trichloride PC13 at temperatures above 300C~ .:
A process for the preparation of a mixture of dichloro-phenylphosphane C6HsPCl2 and chlorodiphenylphosphane :~ ( C6Hs ) 2 PCl in which triphenylphosphane (C6Hs)3P and phos-phorus trichloride PCl3 are reacted at temperatures of 320 to 700C in an autoclave or in a quartz tube in an electric furnace is known from US-A-4 521 347.
: The disadvantage of the known process is that the reac-tion product contains white phosphorus, which makes , 15 working up of the reaction product by distillation very ', difficult.
; The object of the present invention is therefore to ! provide à process for the preparation of chlorophenyl-phosphanes by reaction of triphenylphosphane and phos-! 20 phorus trichloride at temperatures above 300C in which :the reaction product obtained is free from white phos-phorus. This is achieved according to the invention by ~, introducing liquid triphenylphosphane and gaseous phos-phorus trichloride in the given molar ratio at the top of '~ 25 a vertically arranged, elongated and heated reaction .4 zone; by transferring the reaction product discharged at j the foot of the reaction zone to a residence zone charged wlth phosphorus pentachloride; and by removing the excess phosphorus trichloride from the reaction product, via a .
subsequen~ fractionating zone, by heating the residence ,~ zone.
. The process according to the invention fur-thermore can optionally also be carried out such that .:
~ 21~9~
'4; .' 2 a) the reaction zone comprise.s an electrically heatable silicon/silicon carbide tube;
b) the reaction zone is at least partly filled with .;' bulk material comprising granular silicon carbide;
5 c) the silicon carbide of the bulk material has parti- -! cle sizes of 2 to 8 mm, preferably 3 to 6 mm;
.
d) the reaction zone in the region of the silicon . carbide bulk material has temperatures of 350 to 650C, preferably 500 to 600C.
The reaction product obtained by the process according to the invention evidently contains no whit~ phosphorus ~: because it has reacted with the phosphorus pentachloride in the residence zone.
' !, : A plant for carrying out the process according to the ~: 15 invention is shown in diagram form and in section in the attached drawing.
Liquid phosphorus trichloride is fed from a reservoir 1 by a Eirst pump 2 to an evaporator 3 which is joined in the direction of flow to the upper end of a vertically arranged electrically heatable tube 4 made of SiSiC.
Liquid triphenylphosphane is also metered Erom a tank 5, provided with a heating jacket, via a second pump 6 into the upper end of this tube 4, which i~ at least partly filled with a bulk material comprising silicon carbide.
The reaction product discharged from the lower end of the ~: . tube 4 passes into a residence tank 7, which is provided with a heating device and contains phosphorus pentachlor-ide. The contents of the xesidence tank 7 are kept at a temperatuxe above 80C, the phosphorus trichloride flowing out of the residence tank 7 in gaseous form being distilled of:E over a column 8, liquefied in a condenser 9 and collected in a tank 10.
~:
, j :'j I
21~3~
E ~mple 1 (Comparison E~ample) /2041 g (14.9 mol) of PCl3 were metered from a reservoir 1 (cf. the figure) with the aid of a first pump 2 into an evaporator 3 in the course of 3 hours. The gaseous PCl3 flowing out of the evaporator 3 entered a vertically arranged tube 4~ which was made of SiSiC and was heated electrically at 590C and which contained a bulk material comprising silicon carbide. At the same time, 6816 g I(3.11 mol) of liquid Ph3P were introduced from a tank 5, ¦10 provided with a heating jacket, via a second pump into the top of the tube 4. The reaction product collecting in a residence tank 7 was kept at a temperature of at least 80C in this tank, which meant that a large proportion of the excess PC13 distilled off over a column 8/ and was liquefied in a condenser 9 and collected in a tank 10.
`The distillation of the PCl3-depleted reaction product `!,gave the following substances, in addition to further unreacted PCl3-1284 g (7.2 mol) of PhPCl2 250 g (1.1 mol) of Ph2PCl 86.7 g (0.77 mol) of PhCl 3.3 ~ (27 mmol) of P4 37.7 g (144 mol) of Ph3P
i ~
Example 2 (Comparison Example) ~ ;
Example 1 was repeated with the modifications that the tube 4 was heated electrically at 580C and that 800 g (3.05 mol) of liquid Ph3P were introduced into the top of ~` the tube 4.
- Distillation of the PCl3-depleted reaction product gave `~30 the following substances, in addition to further unre-acted PCl3:
I
" :
.,~
~ . , 0~3~
" . .
The present invention relates to a process for the preparation of chlorophenylphosphanes of the formula (C5Hs)n PC13 n ~ in which n is 1 or 2, by reaction of triphenylphosphane i. 5 (C6H5)3P and phosphorus trichloride PC13 at temperatures above 300C~ .:
A process for the preparation of a mixture of dichloro-phenylphosphane C6HsPCl2 and chlorodiphenylphosphane :~ ( C6Hs ) 2 PCl in which triphenylphosphane (C6Hs)3P and phos-phorus trichloride PCl3 are reacted at temperatures of 320 to 700C in an autoclave or in a quartz tube in an electric furnace is known from US-A-4 521 347.
: The disadvantage of the known process is that the reac-tion product contains white phosphorus, which makes , 15 working up of the reaction product by distillation very ', difficult.
; The object of the present invention is therefore to ! provide à process for the preparation of chlorophenyl-phosphanes by reaction of triphenylphosphane and phos-! 20 phorus trichloride at temperatures above 300C in which :the reaction product obtained is free from white phos-phorus. This is achieved according to the invention by ~, introducing liquid triphenylphosphane and gaseous phos-phorus trichloride in the given molar ratio at the top of '~ 25 a vertically arranged, elongated and heated reaction .4 zone; by transferring the reaction product discharged at j the foot of the reaction zone to a residence zone charged wlth phosphorus pentachloride; and by removing the excess phosphorus trichloride from the reaction product, via a .
subsequen~ fractionating zone, by heating the residence ,~ zone.
. The process according to the invention fur-thermore can optionally also be carried out such that .:
~ 21~9~
'4; .' 2 a) the reaction zone comprise.s an electrically heatable silicon/silicon carbide tube;
b) the reaction zone is at least partly filled with .;' bulk material comprising granular silicon carbide;
5 c) the silicon carbide of the bulk material has parti- -! cle sizes of 2 to 8 mm, preferably 3 to 6 mm;
.
d) the reaction zone in the region of the silicon . carbide bulk material has temperatures of 350 to 650C, preferably 500 to 600C.
The reaction product obtained by the process according to the invention evidently contains no whit~ phosphorus ~: because it has reacted with the phosphorus pentachloride in the residence zone.
' !, : A plant for carrying out the process according to the ~: 15 invention is shown in diagram form and in section in the attached drawing.
Liquid phosphorus trichloride is fed from a reservoir 1 by a Eirst pump 2 to an evaporator 3 which is joined in the direction of flow to the upper end of a vertically arranged electrically heatable tube 4 made of SiSiC.
Liquid triphenylphosphane is also metered Erom a tank 5, provided with a heating jacket, via a second pump 6 into the upper end of this tube 4, which i~ at least partly filled with a bulk material comprising silicon carbide.
The reaction product discharged from the lower end of the ~: . tube 4 passes into a residence tank 7, which is provided with a heating device and contains phosphorus pentachlor-ide. The contents of the xesidence tank 7 are kept at a temperatuxe above 80C, the phosphorus trichloride flowing out of the residence tank 7 in gaseous form being distilled of:E over a column 8, liquefied in a condenser 9 and collected in a tank 10.
~:
, j :'j I
21~3~
E ~mple 1 (Comparison E~ample) /2041 g (14.9 mol) of PCl3 were metered from a reservoir 1 (cf. the figure) with the aid of a first pump 2 into an evaporator 3 in the course of 3 hours. The gaseous PCl3 flowing out of the evaporator 3 entered a vertically arranged tube 4~ which was made of SiSiC and was heated electrically at 590C and which contained a bulk material comprising silicon carbide. At the same time, 6816 g I(3.11 mol) of liquid Ph3P were introduced from a tank 5, ¦10 provided with a heating jacket, via a second pump into the top of the tube 4. The reaction product collecting in a residence tank 7 was kept at a temperature of at least 80C in this tank, which meant that a large proportion of the excess PC13 distilled off over a column 8/ and was liquefied in a condenser 9 and collected in a tank 10.
`The distillation of the PCl3-depleted reaction product `!,gave the following substances, in addition to further unreacted PCl3-1284 g (7.2 mol) of PhPCl2 250 g (1.1 mol) of Ph2PCl 86.7 g (0.77 mol) of PhCl 3.3 ~ (27 mmol) of P4 37.7 g (144 mol) of Ph3P
i ~
Example 2 (Comparison Example) ~ ;
Example 1 was repeated with the modifications that the tube 4 was heated electrically at 580C and that 800 g (3.05 mol) of liquid Ph3P were introduced into the top of ~` the tube 4.
- Distillation of the PCl3-depleted reaction product gave `~30 the following substances, in addition to further unre-acted PCl3:
I
" :
.,~
~ . , 0~3~
" . .
i~ 1189 g (6.6 .mol) of PhPC12 ./. 261 g (1.2 mol) of Ph2PCl 64.4 g (0~57 mol) of PhCl ~? 2.2 g (18 mmol) of P4 S 65.3 g (0.25 mol) of Ph3P
.
~ Example 3 ~Comparison Example) ;, .,1 Example 1 was repeated with the modifications that the ,~4 tube 4 was heated electrically at 600C, that 2905 g (21.2 mol) of PCl3 were metered into the evaporator 3 and that 504 g (1.92 mol) of Ph3P were introduced into the top of the tube 4. Distillation of the PCl3 depleted reaction product gave the following substances, in addition to further unreacted PCl3:
690 g (3.9 mol) of PhPC12 46 g (0.21 mol) of Ph~PCl 86.6 g (0.77 mol) of PhCl 4.3 g (35 mmol) of ~4 < 0.1 g of Ph3P
Example 4`(according to the invention) ~.~
Example 1 was repeated with the modifications that 2473 g (18.0 mol) of PCl3 were reacted with 965 g (3.68 mol3 of Ph3P and that 70 g (0.34 mol) of ~Cls (about 100 % excess, based on the P4 content, detectable by 31P-NMR spectro-scopy, of the crude mixture in the residence tank 7~ were initially introduced into the residence tank 7.
Distillation of the PCl3-depleted reaction product gave ~; the following substances, in addition to further unr~-: acted PCl3:
1460 g (8.16 mol) of PhPCl2 201 g (0.91 mol) of Ph2PCl 115.1 g (1.02 mol) of PhCl !;`,~ ~ 1 g ~ P~l ~ 22.8 g (87 mmol) of Ph3P
!; ' ?. " ~
2 1 ~
Example 5 (according to the invention) ,Example 1 was repeated with the modifications that 2002 g `i(1~o6 mol) of PCl3 were reacted with 806 g (3.07 mol) of Ph3P and that 95 g (0.46 mol) of PCls (about 150 % excess, based on the P4 content, detectable by 3~P-NMR spectro-`scopy, of the crude mixture in the r0sidence tank 7) were initially introduced into the residence tan~ 7.
Distillation of the PCl3-depleted reaction product gave the following substances, in addition to further unre-~0 acted PCl3:
,;1298 g (7.25 mol) of PhPCl2 214 g (0.97 mol) of Ph2PCl i91.5 g (0.81 mol) of PhCl ,i < 0.1 g Of P4 :~i 15 37.0 g (141 mmol) of Ph3P
r,`
:q i s~i ~,~i ' .
- ~, .1 . ~ ~
: ! :
.
~ Example 3 ~Comparison Example) ;, .,1 Example 1 was repeated with the modifications that the ,~4 tube 4 was heated electrically at 600C, that 2905 g (21.2 mol) of PCl3 were metered into the evaporator 3 and that 504 g (1.92 mol) of Ph3P were introduced into the top of the tube 4. Distillation of the PCl3 depleted reaction product gave the following substances, in addition to further unreacted PCl3:
690 g (3.9 mol) of PhPC12 46 g (0.21 mol) of Ph~PCl 86.6 g (0.77 mol) of PhCl 4.3 g (35 mmol) of ~4 < 0.1 g of Ph3P
Example 4`(according to the invention) ~.~
Example 1 was repeated with the modifications that 2473 g (18.0 mol) of PCl3 were reacted with 965 g (3.68 mol3 of Ph3P and that 70 g (0.34 mol) of ~Cls (about 100 % excess, based on the P4 content, detectable by 31P-NMR spectro-scopy, of the crude mixture in the residence tank 7~ were initially introduced into the residence tank 7.
Distillation of the PCl3-depleted reaction product gave ~; the following substances, in addition to further unr~-: acted PCl3:
1460 g (8.16 mol) of PhPCl2 201 g (0.91 mol) of Ph2PCl 115.1 g (1.02 mol) of PhCl !;`,~ ~ 1 g ~ P~l ~ 22.8 g (87 mmol) of Ph3P
!; ' ?. " ~
2 1 ~
Example 5 (according to the invention) ,Example 1 was repeated with the modifications that 2002 g `i(1~o6 mol) of PCl3 were reacted with 806 g (3.07 mol) of Ph3P and that 95 g (0.46 mol) of PCls (about 150 % excess, based on the P4 content, detectable by 3~P-NMR spectro-`scopy, of the crude mixture in the r0sidence tank 7) were initially introduced into the residence tan~ 7.
Distillation of the PCl3-depleted reaction product gave the following substances, in addition to further unre-~0 acted PCl3:
,;1298 g (7.25 mol) of PhPCl2 214 g (0.97 mol) of Ph2PCl i91.5 g (0.81 mol) of PhCl ,i < 0.1 g Of P4 :~i 15 37.0 g (141 mmol) of Ph3P
r,`
:q i s~i ~,~i ' .
- ~, .1 . ~ ~
: ! :
Claims (7)
1. A process for the preparation of chlorophenylphos-phanes of the formula (C6H5)n PCl3-n in which n is 1 or 2, by reaction of triphenylphos-phane (C6H5)3P and phosphorus trichloride PCl3 at temperatures above 300°C, which comprises introduc-ing liquid triphenylphosphane and gaseous phosphorus trichloride in the given molar ratio at the top of a vertically arranged, elongated and heated reaction zone; transferring the reaction product discharged at the foot of the reaction zone to a residence zone charged with phosphorus pentachloride; and removing the excess phosphorus trichloride from the reaction product, via a subsequent fractionating zone, by heating the residence zone.
2. The process as claimed in claim 1, wherein the reaction zone comprises an electrically heatable silicon/silicon carbide tube.
3. The process as claimed in claim 1, wherein the reaction zone is at least partly filled with a bulk material comprising granular silicon carbide.
4. The process as claimed in claim 3, wherein the silicon carbide of the bulk material has particle sizes of 2 to 8 mm.
5. The process as claimed in claim 3, wherein the silicon carbide of the bulk material has particle sizes of 3 to 6 mm.
6. The process as claimed in claim 3, wherein the reaction zone in the region of the silicon carbide bulk material has temperatures of 350 to 650°C.
7. The process as claimed in claim 3, wherein the reaction zone in the region of the silicon carbide bulk material has temperatures of 500 to 600°C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19924238711 DE4238711A1 (en) | 1992-11-17 | 1992-11-17 | Process for the production of chlorophenylphosphines |
| DEP4238711.6 | 1992-11-17 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2109349A1 true CA2109349A1 (en) | 1994-05-18 |
Family
ID=6473050
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2109349 Abandoned CA2109349A1 (en) | 1992-11-17 | 1993-10-27 | Process for the preparation of chlorophenylphosphanes |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0599044B1 (en) |
| JP (1) | JP3578475B2 (en) |
| CA (1) | CA2109349A1 (en) |
| DE (2) | DE4238711A1 (en) |
| DK (1) | DK0599044T3 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19640465A1 (en) * | 1996-09-30 | 1998-04-02 | Basf Ag | Process for the preparation of phenylchlorophosphines |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3216381A1 (en) * | 1982-05-03 | 1983-11-03 | Hoechst Ag, 6230 Frankfurt | METHOD FOR PRODUCING CHLORINE-PHENYL-PHOSPHANES |
-
1992
- 1992-11-17 DE DE19924238711 patent/DE4238711A1/en not_active Withdrawn
-
1993
- 1993-10-16 EP EP19930116741 patent/EP0599044B1/en not_active Expired - Lifetime
- 1993-10-16 DE DE59308865T patent/DE59308865D1/en not_active Expired - Fee Related
- 1993-10-16 DK DK93116741T patent/DK0599044T3/en active
- 1993-10-27 CA CA 2109349 patent/CA2109349A1/en not_active Abandoned
- 1993-11-15 JP JP28520293A patent/JP3578475B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06220073A (en) | 1994-08-09 |
| EP0599044A1 (en) | 1994-06-01 |
| DK0599044T3 (en) | 1999-05-17 |
| DE59308865D1 (en) | 1998-09-17 |
| EP0599044B1 (en) | 1998-08-12 |
| JP3578475B2 (en) | 2004-10-20 |
| DE4238711A1 (en) | 1994-05-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Dead |