GB2037760A - New process for the preparation of L-lysine carbamate - Google Patents
New process for the preparation of L-lysine carbamate Download PDFInfo
- Publication number
- GB2037760A GB2037760A GB7942236A GB7942236A GB2037760A GB 2037760 A GB2037760 A GB 2037760A GB 7942236 A GB7942236 A GB 7942236A GB 7942236 A GB7942236 A GB 7942236A GB 2037760 A GB2037760 A GB 2037760A
- Authority
- GB
- United Kingdom
- Prior art keywords
- lysine
- filtrate
- carbamate
- lysine carbamate
- methanol
- 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
- XFQCPHGOMQULNH-JEDNCBNOSA-N carbamic acid;(2s)-2,6-diaminohexanoic acid Chemical compound NC(O)=O.NCCCC[C@H](N)C(O)=O XFQCPHGOMQULNH-JEDNCBNOSA-N 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims description 10
- 238000002360 preparation method Methods 0.000 title claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 36
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- BVHLGVCQOALMSV-JEDNCBNOSA-N L-lysine hydrochloride Chemical compound Cl.NCCCC[C@H](N)C(O)=O BVHLGVCQOALMSV-JEDNCBNOSA-N 0.000 claims abstract description 6
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 6
- 239000006229 carbon black Substances 0.000 claims abstract description 5
- 239000002244 precipitate Substances 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 235000011089 carbon dioxide Nutrition 0.000 claims description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 4
- 239000007938 effervescent tablet Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000005587 bubbling Effects 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 3
- 239000003085 diluting agent Substances 0.000 claims 2
- 238000011084 recovery Methods 0.000 claims 1
- 230000003226 decolorizating effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000003826 tablet Substances 0.000 description 4
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000008194 pharmaceutical composition Substances 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Inorganic materials [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 235000019766 L-Lysine Nutrition 0.000 description 2
- 239000004472 Lysine Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 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 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229960001138 acetylsalicylic acid Drugs 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 235000005911 diet Nutrition 0.000 description 1
- 230000037213 diet Effects 0.000 description 1
- 229940068517 fruit extracts Drugs 0.000 description 1
- 230000002496 gastric effect Effects 0.000 description 1
- 235000013905 glycine and its sodium salt Nutrition 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000007968 orange flavor Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
Classifications
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/60—Salicylic acid; Derivatives thereof
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L2/00—Non-alcoholic beverages; Dry compositions or concentrates therefor; Their preparation
- A23L2/40—Effervescence-generating compositions
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/325—Carbamic acids; Thiocarbamic acids; Anhydrides or salts thereof
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K31/00—Medicinal preparations containing organic active ingredients
- A61K31/60—Salicylic acid; Derivatives thereof
- A61K31/618—Salicylic acid; Derivatives thereof having the carboxyl group in position 1 esterified, e.g. salsalate
- A61K31/621—Salicylic acid; Derivatives thereof having the carboxyl group in position 1 esterified, e.g. salsalate having the hydroxy group in position 2 esterified, e.g. benorylate
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K9/00—Medicinal preparations characterised by special physical form
- A61K9/0002—Galenical forms characterised by the drug release technique; Application systems commanded by energy
- A61K9/0007—Effervescent
Abstract
L-lysine carbamate is obtained from L-lysine monohydrochloride (of animal feed grade) by treating an aqueous solution thereof with decolourising carbon black, filtering, adding a strong base followed by methanol to the filtrate, filtering again, treating the filtrate with carbon dioxide, filtering off the precipitate and washing it with methanol.
Description
SPECIFICATION
New process for the preparation of L-lysine carbamate
The present invention relates to a new and more economical process for preparing L-lysine carbamate.
The L-lysine carbamate is especially used as an ingredient in effervescent mixtures, which mixtures are themselves used to prepare for example fizzy drinks and effervescent pharmaceutical compositions, such as effervescent cachets or tablets, etc. A particular application is in effervescent pharmaceutical compositions containing no or only very little alkaline ions. This type of pharmaceutical composition indeed removes the undesirable possibility of alkaline ions accumulating in the human system and permits to treat patients following a sodium free diet.
Other advantages of the use of L-lysine carbamate reside in the fact that the gastric tolerance is excellent due to a bufferred medium, and in the virtually immediate passage into the blood system.
The Applicant has now discovered, according to the invention, a new process for preparing the L-lysine carbamate authorizing the choice as a starting product of an L-lysine monohydrochloride of feed grade, and therefore relatively inexpensive.
Said monohydrochloride is, in a first step, treated as an aqueous solution with decolourizing carbon black, which is thereafter eliminated, by filtration for example.
A second step consists in treating the L-lysine monohydrochloride with a base, such as KOH or NaOH, and in eliminating the resulting salt, potassium or sodium chloride for example, by a known technique (spin-drying for example) following the addition of methanol as preferred solvent.
The third step of the process according to the invention consists in treating the filtrate obtained at the second step with carbon dioxide (or with dry ice) and in recovering the resulting precipitate which is the desired product.
The L-lysine carbamate obtained this way is in the form of a white crystalline powder; this product is very soluble in water but it is insoluble in methanol which permits the washing of the precipitate in said methanol
Without the scope of the invention being in any way limited by such an assumption, the Applicant considers as probable that the L-lysine carbamate resulting from the association of a mole of L-lysine with a mole of Co2 is stabilized by a second mole of L-lysine according to the following formula:
HOOC(NH2)CH- (CH2)4 - NH - COOH NH2(CH2)4 - CH(NH2)COOH this being confirmed by the results of the analyses effected. The following examples illustrate the invention without however limiting its scope.
Example 1
300 g of "feed grade" L-lysine monohydrochloride (i.e. of animal feed grade (titer > 98%) are dissolved in 300 cm3 of water at between 50 and 60"C.
The mixture is stirred for 15 minutes at 60"C with 6 g of decolourizing carbon black.
Then it is filtered on paper.
110g of KOH are added gradually at about 40do, whilst stirring, the mixture is cooled down to room temperature and then stirred for one hour. 1500cm3 of or methanol are gradually added and the mixture is stirred for 2 hours and 30 minutes, following which the potassium chloride which has formed is spin-dried.
60 to 80 g of carbon dioxide are gradually added to the filtrate over a one-hour period approximately, and the mixture is left to stand overnight, then it is filtered and washed in methanol at 95% and dried at about 40"C. 200 g of the desired product are obtained.
M.P. 249 - 250.
Analysis: C13H28N406
Calculated: C%46.41 H%8.39N%16.65
0%28.54
Found: C % 46.62 H % 8.37 N % 16.39
0% 28.33
Example 2
300 g of "feed grade" L-lysine monohydrochloride (titer > 98%) are dissolved in 450 of water at 30"C.
The solution is stirred for 15 minutes at 30"C with 6 g of decolourizing carbon black.
Then it is filtered on paper.
79 g of sodium hydroxide are gradually added at about 20"C and the mixture is left to cool down to room temperature and then stirred for 1 hour. 2000cm3 of or methanol are then added gradually and the mixture is stirred for 3 hours, following which the sodium chloride which has formed is spin-dried.
60 to 80 g of carbon dioxide are added gradually to the filtrate, over a one-hour period approximately, and
the mixture is left to stand overnight, then it is filtered and washed in methanol at 95% and dried at about 40"C. 189 g of the desired product are obtained.
M.P. 246-250.
Analysis: C13H28N406
Calculated C % 46.41 H % 8.39 % N % 16.65
0%28.54
Found: C % 46.23 H % 8.43 N % 16.67
0 % 28.29
Example 3
The same method is used as in Example 1, except that the bubbling of CO2 is replaced bythe gradual introduction of dry ice, until there is no more white precipitate forming. The mixture is then left to cool down to room temperature and stirred for 3 hours and 30 minutes. The resulting product is filtered before being washed in 800 cm3 of methanol, which gives the desired product with a yield of 192 g. M.P. 247-250"C.
Example4
Effervescent tablets containing acetylsalicyclic acid, without alkaline ions.
An effervescent mixture is prepared in the following proportions:
acetylsalicyclic acid . . 0.500 g
L-lysine carbamate . . 1.6g citric acid . . 0.4g These values are given for a tablet dosed in a conventional manner at 0.5 g of acetylsalicylic acid.
Example 5
An effervescent composition for a fizzy drink is prepared in the following proportions:
sugar . . 179 L-lysine carbamate . . 1.4 9 citric acid . . 2.7 9 which can be flavoured in known manner with fruit extracts in powder form. vitamin c may also be added if necessary when orange flavour is used.
Example 6
Preparation of effervescent tablets dosed at 0.5 g of phosphorus
The following formula can be used, for example:
L-lysine carbamate . . 1.4 9 glycocoll phosphate . . . . . 1.3979 anhydrous magnesium monobasic phosphate . . 0.881 g.
The tablets of Examples 4 and 6 are prepared in a manner known by any one skilled in the art by separate drying up of the components, sifting, mixing and moulding into tablets.
The therapeutical effects, the doses and routes of administration of such preparations are also known.
Claims (7)
1. A process for the preparation of L-lysine carbamate, consisting in the following steps:
(a) treatment of an aqueous solution of "feed grade" L-lysine monohydrochloride, titer greater than 98% with decolourizing carbon black, under stirring;
(b) filtration, on paperforexample; (c) addition of a strong base to the filtrate, then of methanol, and filtration;
(d) treatment of the filtrate with carbon dioxide;
(e) filtration, methanol washing of the precipitate, and recovery of same.
2. A process as claimed in claim 1, wherein the strong base added at step (c) is potassium or sodium hydroxide.
3. A process as claimed in claim 1 or 2, wherein the step (d) consists in a bubbling of carbon dioxide in the filtrate or in a gradual introduction of dry ice in said filtrate.
4. A process for the preparation of L-lysine carbamate substantially as herein before described with reference to Examples 1,2 or 3.
5. L-lysine carbamate obtained by the process claimed in any one of claims 1 to 4.
6. An effervescent tablet for pharmaceutical or veterinary purposes, comprising L-lysine carbamate according to claim 5 as effervescing agent together with a pharmaceutical or veterinary agent, and optionally one or more diluent, carrier or flavouring.
7. An effervescent composition for a fizzy drink, comprising L-lysine carbamate according to claim 5 as effervescing agent, and a sweetner, together optionally with one or more diluent, carrier or flavouring.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR7836011A FR2444665B1 (en) | 1978-12-21 | 1978-12-21 | NEW PROCESS FOR THE PREPARATION OF L-LYSINE CARBAMATE |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB2037760A true GB2037760A (en) | 1980-07-16 |
| GB2037760B GB2037760B (en) | 1983-05-11 |
Family
ID=9216407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB7942236A Expired GB2037760B (en) | 1978-12-21 | 1979-12-07 | Process for the preparation of l-lysine carbamate |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5587753A (en) |
| BE (1) | BE880749A (en) |
| DE (1) | DE2951132A1 (en) |
| ES (1) | ES487158A1 (en) |
| FR (1) | FR2444665B1 (en) |
| GB (1) | GB2037760B (en) |
| IT (1) | IT1119633B (en) |
| LU (1) | LU82007A1 (en) |
| NL (1) | NL7909081A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4760138A (en) * | 1984-12-13 | 1988-07-26 | Nestec S. A. | Carbonating agents and their preparation |
| EP0336987A1 (en) * | 1988-04-12 | 1989-10-18 | Mitsubishi Kasei Corporation | Feed additive for ruminants |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2215950A2 (en) * | 1973-02-01 | 1974-08-30 | Union Pharma Scient Appl | Carbonated lysine - as carbonate source in effervescent compositions |
-
1978
- 1978-12-21 FR FR7836011A patent/FR2444665B1/en not_active Expired
-
1979
- 1979-12-07 GB GB7942236A patent/GB2037760B/en not_active Expired
- 1979-12-17 JP JP16395479A patent/JPS5587753A/en active Granted
- 1979-12-17 NL NL7909081A patent/NL7909081A/en not_active Application Discontinuation
- 1979-12-18 LU LU82007A patent/LU82007A1/en unknown
- 1979-12-19 DE DE19792951132 patent/DE2951132A1/en active Granted
- 1979-12-20 ES ES487158A patent/ES487158A1/en not_active Expired
- 1979-12-20 IT IT69447/79A patent/IT1119633B/en active
- 1979-12-20 BE BE2/58288A patent/BE880749A/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4760138A (en) * | 1984-12-13 | 1988-07-26 | Nestec S. A. | Carbonating agents and their preparation |
| EP0336987A1 (en) * | 1988-04-12 | 1989-10-18 | Mitsubishi Kasei Corporation | Feed additive for ruminants |
| US4937083A (en) * | 1988-04-12 | 1990-06-26 | Mitsubishi Chemical Industries Limited | Feed additive for ruminants |
Also Published As
| Publication number | Publication date |
|---|---|
| IT7969447A0 (en) | 1979-12-20 |
| BE880749A (en) | 1980-06-20 |
| IT1119633B (en) | 1986-03-10 |
| ES487158A1 (en) | 1980-09-16 |
| NL7909081A (en) | 1980-06-24 |
| LU82007A1 (en) | 1980-07-21 |
| FR2444665A1 (en) | 1980-07-18 |
| GB2037760B (en) | 1983-05-11 |
| JPS5587753A (en) | 1980-07-02 |
| DE2951132A1 (en) | 1980-07-10 |
| FR2444665B1 (en) | 1985-06-28 |
| JPS6320220B2 (en) | 1988-04-26 |
| DE2951132C2 (en) | 1988-12-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 746 | Register noted 'licences of right' (sect. 46/1977) | ||
| 732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) | ||
| 732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) | ||
| PE20 | Patent expired after termination of 20 years |
Effective date: 19991206 |