CA2157545A1 - Process for preparing alkyl polyglycosides - Google Patents
Process for preparing alkyl polyglycosidesInfo
- Publication number
- CA2157545A1 CA2157545A1 CA002157545A CA2157545A CA2157545A1 CA 2157545 A1 CA2157545 A1 CA 2157545A1 CA 002157545 A CA002157545 A CA 002157545A CA 2157545 A CA2157545 A CA 2157545A CA 2157545 A1 CA2157545 A1 CA 2157545A1
- Authority
- CA
- Canada
- Prior art keywords
- carried out
- transglycosidation
- tubular reactor
- alkyl
- alcohol
- 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
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
- C07H15/02—Acyclic radicals, not substituted by cyclic structures
- C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Biochemistry (AREA)
- Biotechnology (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Molecular Biology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Saccharide Compounds (AREA)
Abstract
The invention relates to a novel process for preparing alkyl polyglycosides from alkyl glycosides having C1 to C6 alkyl radicals and alcohols having 8 to 20 C atoms by acid-catalysed transglycosidation. The reaction is carried out using a tubular reactor under co-current flow conditions.
Description
2157~5 - HULS AKTIENGESELLSCHAFT - 1 - O.Z. 4863 - Patentabteilung -Process for preparinq alkyl polyqlycosides The invention relates to a novel process for preparingalkyl polyglycosides having C8 to C20 alkyl radicals from alkyl glycosides having Cl to C6 alkyl radicals and alco-hols having 8 to 20 C atoms by acid-catalysed transglyco-sidation.
Alkyl polyglycosides having C8 to C20 alkyl radicals can be prepared in whole or in part from renewable raw materials. The alkyl polyglycosides, because of their interesting surfactant properties with simultaneously very good biodegradability are becoming increasingly important. For applications in the home and the cosmetics sector these products must satisfy high aesthetic requirements. There is therefore interest in processes by which alkyl polyglycosides can be prepared in transparent aqueous solutions of unobjectionable colour.
To prepare alkyl polyglycosides having long-chain alkyl groups, alkyl glycosides having Cl to C6 alkyl groups can first be prepared by glycosidation of saccharides having short-chain alcohols. These products are then converted into the desired alkyl polglycosides by transglycosida-tion using long-chain alcohols at elevated temperature.
However, the products thus prepared are dark in colour.
Reeping to defined mass ratios and with the use of solubilizers, the polar saccharides can also be reacted directly with the nonpolar long-chain alcohols to give the alkyl polyglycosides. In this case also, without the addition of colour improvers, if the reaction is carried out in the stirred tank, dark-coloured products are obtained.
In EP 0 077 167, a single-stage preparation process is described in which an aldose or a ketose is reacted directly with a long-chain alcohol in the molar ratio of 1:1.25 to 1:4. The reaction is carried out at low water ~575~
contents in the presence of a reducing agent.
This single-stage process is improved in DE-A-41 01 252 by a large excess of alcohol being used and alkali metal hydroxide dissolved in alcohols being used for the neutralization. The reaction is carried out here in a stirred tank.
In addition, it is known that the colour quality of the alkyl polyglycosides can be improved by measures relating to equipment.
Thus, according to EP-A-0 482 325, in a two-stage preparation process, the first stage, the glycosidation of saccharides in aqueous solution using Cl to C6 alcohols, can be carried out in a counter-current flow reaction column, for example in a bubble-cap column.
Moreover, according to DE-A-41 16 665, the trans-glycosidation, the second stage of the two-stage process, can also be carried out in a reaction column and preferably under counter-current flow conditions.
These processes can be still further improved and simplified with respect to the reactors.
It is attempted according to the present invention to simplify further the transglycosidation in a two-stage process.
Thus, according to the invention, the transglycos-idation is carried out using a tubular reactor under co-current flow conditions.
Suitable tubular reactors generally have a diameter 21~7~4~
- - 2a -of 0.5 to 50 cm and a length of 0.5 to 50 m, where the length is to be at least four times the diameter. In the simplest case this is a heatable tube. Preferably, however, the tubular reactor also has a plurality of 21~7545 - - 3 - O.Z. 4863 nozzles via which the readily volatile substances can be taken off or expelled by means of a vacuum or using an inert gas stream, respectively.
The tubular reactor can also contain chicanes and turbu-lence-generating internals. The tube can be arranged horizontally, at an incline or vertically. However, columns are not considered as tubular reactors in the context of this invention.
The saccharide moiety of the alkyl glycosides used can be derived from aldoses or ketoses. Examples of these are glucose, mannose, galactose and fructose, glucose being preferably used. The alkyl radicals which are suitable are for example methyl, ethyl, butyl or hexyl.
Alcohols which are suitable for the present process are, for example, octanol, decanol, lauryl alcohol, myristyl alcohol, palmityl alcohol and stearyl alcohol. Mixtures of alcohols can also be used. Preferably, alcohols having 8 to 12 C atoms are used.
The alkyl glycoside/alcohol molar ratio is preferably in the range from 1:2 to 1:10.
The catalysts which are suitable are mineral acids and strong organic acids. Examples of these are sulphuric acid, phosphoric acid and p-toluenesulphonic acid. The catalyst is preferably used in concentrations of 0.2 to 5%, based on the saccharide.
The reaction is usually carried out at a temperature of 70 to 140C, temperatures of 100 to 140C being parti-cularly preferred.
Simultaneously, a mean residence time of 5 to 90 minutes is preferably set.
The process is preferably carried out continuously. The ~57~S
- 4 - O.Z. 4863 products generally have a mean degree of glycosidation of 1 to 10, mean degrees of glycosidation of 1.1 to 4 being particularly preferably set. Very particular preference is given to mean degrees of glycosidation of 1.1 to 1.5.
By means of the present invention, in particular in the case of continuously operating synthesis plants, the expenditure in terms of apparatus is greatly decreased.
The yield is increased and the space-time yield is improved. Owing to the short residence times and the narrow residence time distributions, because of the low thermal stress, light products of high quality are obtained. The products are of light colour if their 50%
strength aqueous solutions before H2O2 bleaching have iodine colour values of ~60.
After the reaction the product is neutralized with a base in a known manner, whereupon excess fatty alcohol is separated off by distillation. The residual fatty alcohol content is then generally below 1%. The product is then generally mixed with water and bleached using H2O2.
When the invention is carried out in practice, stirred tanks can also be provided upstream or downstream of the tubular reactor. Thus the alkyl glycosides can react in part with the long-chain alcohols for example in an upstream tubular reactor. The reaction mixture is then homogenized and passed into the tubular reactor. Down-stream stirred reactors generally only serve to increase the residence time and to complete the conversion.
Preferably, 5 to 80% of the reaction is carried out in a tubular reactor.
Example A stirred reactor is continuously charged with 40 kg/h of fatty alcohol mixture comprising 68% of dodecanol, 26% of tetradecanol and 6~ of hexadecanol, and with 20 kg/h of butanolic butyl glucoside solution which contains 65% of 1 54~
~ - S - O.Z. 4863 butanol and 35% of butyl glucoside. A mean residence time of 3.5 hours is set. By adding p-toluenesulphonic acid, a catalyst concentration of 0.25 per cent by weight is maintained in the reaction mixture. At 115C and 5 mbar, approximately 13 kg/h of butanol are distilled off via a column. 47 kg of reaction mixture which contains 77% of fatty alcohol, 11.1% of Cl2 to Cl6 alkyl glucoside and 0.63% of butyl glucoside leave the stirred reactor per hour.
This reaction mixture is passed at 112C through a tube having an internal diameter of 25 cm and a length of 200 cm. When the theoretical residence time is approx-imately 30 minutes, at the end of the tubular reactor there is obtained a mixture which contains 76.5% of fatty alcohol, 11.7% of Cl2 to Cl6 alkyl glucoside and 0.26% of butyl glucoside. The mean degree of glycosidation of the alkyl glucoside is 1.2.
Alkyl polyglycosides having C8 to C20 alkyl radicals can be prepared in whole or in part from renewable raw materials. The alkyl polyglycosides, because of their interesting surfactant properties with simultaneously very good biodegradability are becoming increasingly important. For applications in the home and the cosmetics sector these products must satisfy high aesthetic requirements. There is therefore interest in processes by which alkyl polyglycosides can be prepared in transparent aqueous solutions of unobjectionable colour.
To prepare alkyl polyglycosides having long-chain alkyl groups, alkyl glycosides having Cl to C6 alkyl groups can first be prepared by glycosidation of saccharides having short-chain alcohols. These products are then converted into the desired alkyl polglycosides by transglycosida-tion using long-chain alcohols at elevated temperature.
However, the products thus prepared are dark in colour.
Reeping to defined mass ratios and with the use of solubilizers, the polar saccharides can also be reacted directly with the nonpolar long-chain alcohols to give the alkyl polyglycosides. In this case also, without the addition of colour improvers, if the reaction is carried out in the stirred tank, dark-coloured products are obtained.
In EP 0 077 167, a single-stage preparation process is described in which an aldose or a ketose is reacted directly with a long-chain alcohol in the molar ratio of 1:1.25 to 1:4. The reaction is carried out at low water ~575~
contents in the presence of a reducing agent.
This single-stage process is improved in DE-A-41 01 252 by a large excess of alcohol being used and alkali metal hydroxide dissolved in alcohols being used for the neutralization. The reaction is carried out here in a stirred tank.
In addition, it is known that the colour quality of the alkyl polyglycosides can be improved by measures relating to equipment.
Thus, according to EP-A-0 482 325, in a two-stage preparation process, the first stage, the glycosidation of saccharides in aqueous solution using Cl to C6 alcohols, can be carried out in a counter-current flow reaction column, for example in a bubble-cap column.
Moreover, according to DE-A-41 16 665, the trans-glycosidation, the second stage of the two-stage process, can also be carried out in a reaction column and preferably under counter-current flow conditions.
These processes can be still further improved and simplified with respect to the reactors.
It is attempted according to the present invention to simplify further the transglycosidation in a two-stage process.
Thus, according to the invention, the transglycos-idation is carried out using a tubular reactor under co-current flow conditions.
Suitable tubular reactors generally have a diameter 21~7~4~
- - 2a -of 0.5 to 50 cm and a length of 0.5 to 50 m, where the length is to be at least four times the diameter. In the simplest case this is a heatable tube. Preferably, however, the tubular reactor also has a plurality of 21~7545 - - 3 - O.Z. 4863 nozzles via which the readily volatile substances can be taken off or expelled by means of a vacuum or using an inert gas stream, respectively.
The tubular reactor can also contain chicanes and turbu-lence-generating internals. The tube can be arranged horizontally, at an incline or vertically. However, columns are not considered as tubular reactors in the context of this invention.
The saccharide moiety of the alkyl glycosides used can be derived from aldoses or ketoses. Examples of these are glucose, mannose, galactose and fructose, glucose being preferably used. The alkyl radicals which are suitable are for example methyl, ethyl, butyl or hexyl.
Alcohols which are suitable for the present process are, for example, octanol, decanol, lauryl alcohol, myristyl alcohol, palmityl alcohol and stearyl alcohol. Mixtures of alcohols can also be used. Preferably, alcohols having 8 to 12 C atoms are used.
The alkyl glycoside/alcohol molar ratio is preferably in the range from 1:2 to 1:10.
The catalysts which are suitable are mineral acids and strong organic acids. Examples of these are sulphuric acid, phosphoric acid and p-toluenesulphonic acid. The catalyst is preferably used in concentrations of 0.2 to 5%, based on the saccharide.
The reaction is usually carried out at a temperature of 70 to 140C, temperatures of 100 to 140C being parti-cularly preferred.
Simultaneously, a mean residence time of 5 to 90 minutes is preferably set.
The process is preferably carried out continuously. The ~57~S
- 4 - O.Z. 4863 products generally have a mean degree of glycosidation of 1 to 10, mean degrees of glycosidation of 1.1 to 4 being particularly preferably set. Very particular preference is given to mean degrees of glycosidation of 1.1 to 1.5.
By means of the present invention, in particular in the case of continuously operating synthesis plants, the expenditure in terms of apparatus is greatly decreased.
The yield is increased and the space-time yield is improved. Owing to the short residence times and the narrow residence time distributions, because of the low thermal stress, light products of high quality are obtained. The products are of light colour if their 50%
strength aqueous solutions before H2O2 bleaching have iodine colour values of ~60.
After the reaction the product is neutralized with a base in a known manner, whereupon excess fatty alcohol is separated off by distillation. The residual fatty alcohol content is then generally below 1%. The product is then generally mixed with water and bleached using H2O2.
When the invention is carried out in practice, stirred tanks can also be provided upstream or downstream of the tubular reactor. Thus the alkyl glycosides can react in part with the long-chain alcohols for example in an upstream tubular reactor. The reaction mixture is then homogenized and passed into the tubular reactor. Down-stream stirred reactors generally only serve to increase the residence time and to complete the conversion.
Preferably, 5 to 80% of the reaction is carried out in a tubular reactor.
Example A stirred reactor is continuously charged with 40 kg/h of fatty alcohol mixture comprising 68% of dodecanol, 26% of tetradecanol and 6~ of hexadecanol, and with 20 kg/h of butanolic butyl glucoside solution which contains 65% of 1 54~
~ - S - O.Z. 4863 butanol and 35% of butyl glucoside. A mean residence time of 3.5 hours is set. By adding p-toluenesulphonic acid, a catalyst concentration of 0.25 per cent by weight is maintained in the reaction mixture. At 115C and 5 mbar, approximately 13 kg/h of butanol are distilled off via a column. 47 kg of reaction mixture which contains 77% of fatty alcohol, 11.1% of Cl2 to Cl6 alkyl glucoside and 0.63% of butyl glucoside leave the stirred reactor per hour.
This reaction mixture is passed at 112C through a tube having an internal diameter of 25 cm and a length of 200 cm. When the theoretical residence time is approx-imately 30 minutes, at the end of the tubular reactor there is obtained a mixture which contains 76.5% of fatty alcohol, 11.7% of Cl2 to Cl6 alkyl glucoside and 0.26% of butyl glucoside. The mean degree of glycosidation of the alkyl glucoside is 1.2.
Claims (7)
1. A process for preparing an alkyl polyglycoside having a C8 to C20 alkyl radical from an alkyl glycoside having a C1 to C6 alkyl radical and an alcohol having 8 to 20 carbon atoms by an acid-catalysed transglycosidation, wherein the transglycosidation is carried out using a tubular reactor under co-current flow conditions.
2. A process according to claim 1, wherein the trans-glycosidation is carried out at 100 to 140°C.
3. A process according to claim 1, wherein a mean residence time of 5 to 90 minutes is set in the reactor.
4. A process according to claim 1, wherein an alcohol having 8 to 12 carbon atoms is used.
5. A process according to claim 1, wherein 5 to 80%
of the transglycosidation is carried out in the tubular reactor.
of the transglycosidation is carried out in the tubular reactor.
6. A process for preparing an alkyl polyglycoside having a C8 to C20 alkyl radical, which comprises:
a transglycosidation of butyl glycoside with an alcohol having 8 to 20 carbon atoms in the presence of an acid catalyst at a temperature of 70 to 140°C and at a butyl glycoside/alcohol molar ratio of 1:2 to 1:10, wherein 5 to 80% of the transglycosidation reaction is carried out under co-current flow conditions in a tubular reactor having a diameter of 0.5 to 50 cm and a length of 0.5 to 50 m, provided that the length is at least four times the diameter, such that a mean residence time in the tubular reactor is 5 to 90 minutes, and wherein the remainder of the transglycosidation reaction is carried out in a stirred reactor upstream or downstream of the tubular reactor.
a transglycosidation of butyl glycoside with an alcohol having 8 to 20 carbon atoms in the presence of an acid catalyst at a temperature of 70 to 140°C and at a butyl glycoside/alcohol molar ratio of 1:2 to 1:10, wherein 5 to 80% of the transglycosidation reaction is carried out under co-current flow conditions in a tubular reactor having a diameter of 0.5 to 50 cm and a length of 0.5 to 50 m, provided that the length is at least four times the diameter, such that a mean residence time in the tubular reactor is 5 to 90 minutes, and wherein the remainder of the transglycosidation reaction is carried out in a stirred reactor upstream or downstream of the tubular reactor.
7. A process according to claim 6, wherein the remainder of the transglycosidation is carried out in the stirred reactor upstream of the tubular reactor; and the resulting reaction mixture is then homogenized and passed into the tubular reactor.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4431856.1 | 1994-09-07 | ||
| DE4431856A DE4431856A1 (en) | 1994-09-07 | 1994-09-07 | Process for the preparation of alkyl polyglycosides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2157545A1 true CA2157545A1 (en) | 1996-03-08 |
Family
ID=6527633
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002157545A Abandoned CA2157545A1 (en) | 1994-09-07 | 1995-09-05 | Process for preparing alkyl polyglycosides |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0702024A1 (en) |
| JP (1) | JPH08176182A (en) |
| KR (1) | KR960010674A (en) |
| CN (1) | CN1128267A (en) |
| CA (1) | CA2157545A1 (en) |
| DE (1) | DE4431856A1 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19710112A1 (en) * | 1997-03-12 | 1998-09-17 | Henkel Kgaa | Process for the continuous production of alkyl and / or alkenyl oligoglycosides |
| CN102861532B (en) * | 2012-09-21 | 2014-03-12 | 浙江大学 | Octadecanol glucose gemini surfactant and preparation method thereof |
| CN102875613B (en) * | 2012-09-21 | 2014-04-16 | 浙江大学 | Hexadecanol glucose dimeric surfactant and preparation method thereof |
| CN102895914B (en) * | 2012-09-21 | 2014-03-12 | 浙江大学 | Dodecanol glucose gemini surfactant and preparation method thereof |
| CN102872752B (en) * | 2012-09-21 | 2014-04-16 | 浙江大学 | Decanol glucose dimeric surfactant and preparation method thereof |
| CN102895915B (en) * | 2012-09-21 | 2014-03-12 | 浙江大学 | Tetradecanol glucose gemini surfactant and preparation method thereof |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4223129A (en) * | 1978-09-01 | 1980-09-16 | A. E. Staley Manufacturing Company | Continuous process for making alkyl aldosides from starch or other carbohydrates |
| US4329449A (en) * | 1978-09-01 | 1982-05-11 | A. E. Staley Manufacturing Company | Method of using recycled mother liquors to produce aldosides |
| ATE15498T1 (en) | 1981-10-08 | 1985-09-15 | Rohm & Haas France | PROCESSES FOR THE PRODUCTION OF SURFACE-ACTIVE GLYCOSIDES AND THEIR USE IN COSMETIC, PHARMACEUTICAL AND HOUSEHOLD PRODUCTS. |
| DE3940827A1 (en) * | 1989-12-11 | 1991-06-13 | Henkel Kgaa | METHOD FOR CONTINUOUSLY BLEACHING LIQUIDS WITH OZONE |
| DE4034074A1 (en) | 1990-10-26 | 1992-04-30 | Huels Chemische Werke Ag | METHOD FOR PRODUCING ALKYL GLYCOSIDES AND ALKYLOLIGOGLYCOSIDES |
| DE4101252A1 (en) | 1991-01-17 | 1992-07-23 | Huels Chemische Werke Ag | METHOD FOR PRODUCING ALKYLGLYCOSIDES AND ALKYLPOLYGLYCOSIDES |
| DE4116665A1 (en) | 1991-05-22 | 1992-11-26 | Huels Chemische Werke Ag | PROCESS FOR THE PREPARATION OF ALKYLPOLYGLYCOSIDES |
-
1994
- 1994-09-07 DE DE4431856A patent/DE4431856A1/en not_active Withdrawn
-
1995
- 1995-07-12 EP EP95110920A patent/EP0702024A1/en not_active Withdrawn
- 1995-09-05 CA CA002157545A patent/CA2157545A1/en not_active Abandoned
- 1995-09-06 CN CN95116218A patent/CN1128267A/en active Pending
- 1995-09-06 KR KR1019950029073A patent/KR960010674A/en not_active Application Discontinuation
- 1995-09-06 JP JP7229348A patent/JPH08176182A/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| KR960010674A (en) | 1996-04-20 |
| EP0702024A1 (en) | 1996-03-20 |
| CN1128267A (en) | 1996-08-07 |
| DE4431856A1 (en) | 1996-03-14 |
| JPH08176182A (en) | 1996-07-09 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| FZDE | Dead |