NL8901701A - PROCESS FOR THE PREPARATION OF LEFT-ROTATING AND RIGHT-ROTATING DROPROPIZINE. - Google Patents
PROCESS FOR THE PREPARATION OF LEFT-ROTATING AND RIGHT-ROTATING DROPROPIZINE. Download PDFInfo
- Publication number
- NL8901701A NL8901701A NL8901701A NL8901701A NL8901701A NL 8901701 A NL8901701 A NL 8901701A NL 8901701 A NL8901701 A NL 8901701A NL 8901701 A NL8901701 A NL 8901701A NL 8901701 A NL8901701 A NL 8901701A
- Authority
- NL
- Netherlands
- Prior art keywords
- dropropizine
- rotating
- preparation
- clockwise
- reaction
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 17
- PTVWPYVOOKLBCG-UHFFFAOYSA-N 3-(4-phenyl-1-piperazinyl)propane-1,2-diol Chemical compound C1CN(CC(O)CO)CCN1C1=CC=CC=C1 PTVWPYVOOKLBCG-UHFFFAOYSA-N 0.000 title claims description 15
- 229960004722 dropropizine Drugs 0.000 title claims description 15
- 238000002360 preparation method Methods 0.000 title claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- YZTJYBJCZXZGCT-UHFFFAOYSA-N phenylpiperazine Chemical compound C1CNCCN1C1=CC=CC=C1 YZTJYBJCZXZGCT-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- CTKINSOISVBQLD-GSVOUGTGSA-N (R)-Glycidol Chemical compound OC[C@@H]1CO1 CTKINSOISVBQLD-GSVOUGTGSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- CTKINSOISVBQLD-VKHMYHEASA-N (S)-Glycidol Chemical compound OC[C@H]1CO1 CTKINSOISVBQLD-VKHMYHEASA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 description 3
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- PTVWPYVOOKLBCG-ZDUSSCGKSA-N levodropropizine Chemical compound C1CN(C[C@H](O)CO)CCN1C1=CC=CC=C1 PTVWPYVOOKLBCG-ZDUSSCGKSA-N 0.000 description 2
- AELLFKPPLQHPRV-UHFFFAOYSA-N n-propan-2-yl-7-propan-2-yliminocyclohepta-1,3,5-trien-1-amine Chemical compound CC(C)NC1=CC=CC=CC1=NC(C)C AELLFKPPLQHPRV-UHFFFAOYSA-N 0.000 description 2
- DFQNMODTAFTGHS-UHFFFAOYSA-N 2,3-dihydroxypropyl 4-methylbenzenesulfonate Chemical compound CC1=CC=C(S(=O)(=O)OCC(O)CO)C=C1 DFQNMODTAFTGHS-UHFFFAOYSA-N 0.000 description 1
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 1
- 239000003434 antitussive agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Werkwijze voor de bereiding van linksdraaiend en rechtsdraaienddropropizineMethod for the preparation of counterclockwise and clockwise dropropizine
De uitvinding heeft betrekking op een nieuwe werkwijzevoor de bereiding van linksdraaiend dropropizine [S(-)-3-(4-fenyl-piperazin-l-yDpropaan-1,2-diol] en van rechtsdraaiend dropropizine[R(+)-3-(4-fenylpiperazin-l-yl)propaan-1,2-diol] met respectievelijkde formules 1 en 2 van het formuleblad .The invention relates to a new process for the preparation of counter-clockwise dropropizine [S (-) - 3- (4-phenyl-piperazin-1-yDpropane-1,2-diol] and of counterclockwise dropropizine [R (+) - 3- (4-phenylpiperazin-1-yl) propane-1,2-diol] of formulas 1 and 2 of the formula sheet, respectively.
De verbindingen met de formules 1 en 2 als ook racemischemengsels daarvan zijn bekend en bruikbaar als middelen tegen hoest.The compounds of formulas 1 and 2 as well as racemic mixtures thereof are known and useful as anti-cough agents.
Volgens de Europese octrooiaanvrage 147847 kunnen deverbindingen met de formules 1 en 2 worden verkregen uit racemischdropropizine door conventionele optische scheidingsmethoden ofworden gesynthetiseerd uit (+)-l,2-isopropylideen-sn-glyceroldat wordt omgezet in het overeenkomstige tosylaat en daarna onderwor¬pen aan deketalisering, onder verkrijging van (-)-glycerol-l-tosylaat,dat met 1-fenylpiperazine wordt gecondenseerd onder verkrijgingvan linksdraaiend dropropizine met formule 1. De rechtsdraaiendevorm met formule 2 wordt verkregen uit {+)-glycerol-l-tosylaat.According to European patent application 147847, the compounds of formulas 1 and 2 can be obtained from racemic dropropizine by conventional optical separation methods or synthesized from (+) - 1,2-isopropylidene-sn-glycerol which is converted to the corresponding tosylate and then decetalized , yielding (-) - glycerol-1-tosylate, which is condensed with 1-phenylpiperazine to yield counter-clockwise dropropizine of formula 1. The counter-clockwise form of formula 2 is obtained from {+) -glycerol-1-tosylate.
Door de betrekkelijk lage opbrengsten en de ingewikkeld¬heid van de verschillende stappen van de reactie zijn de beschrevenwerkwijzen niet zo voordelig, niet zo economisch en niet zo geschiktvoor toepassing op industriële schaal.Due to the relatively low yields and the complexity of the various steps of the reaction, the methods described are not as advantageous, not as economical and not so suitable for industrial scale application.
Een werkwijze voor de bereiding van racemisch dropropizineis bekend uit het Britse octrooischrift 938646. Hierbij laat men1-fenylpiperazine reageren met racemisch glycidol. Deze werkwijzegeeft echter racemisch dropropizine met lage opbrengsten.A process for the preparation of racemic dropropizineis known from British Patent 938646. Herein 1-phenylpiperazine is reacted with racemic glycidol. However, this method produces racemic dropropizine with low yields.
De onderhavige uitvinding voorziet nu in een werkwijzewaarmee op eenvoudige en direkte wijze de afzonderlijke enantiomerenvan dropropizine met formule 1 en 2 worden verkregen, door selectievereactie van 1-fenylpiperazine met (R)-glycidol[(R)-2,3-epoxy-l-propanol] (reactieschema A) of met (S)-glycidol [(S)-2,3-epoxy-1-propanol] (reactieschema B) .The present invention now provides a process by which the individual enantiomers of dropropizine of formulas 1 and 2 are obtained in a simple and direct manner by selection reaction of 1-phenylpiperazine with (R) -glycidol [(R) -2,3-epoxy-1- propanol] (reaction scheme A) or with (S) -glycidol [(S) -2,3-epoxy-1-propanol] (reaction scheme B).
De reacties worden gewoonlijk uitgevoerd in aanwezigheidvan oplosmiddel, zoals water, alkoholen, tolueen of mengsels daarvan.Voorbeelden van alkoholen die als oplosmiddel kunnen worden gebruikt,zijn ethanol, methanol of bij voorkeur isopropanol.The reactions are usually carried out in the presence of a solvent such as water, alcohols, toluene or mixtures thereof. Examples of alcohols which can be used as a solvent are ethanol, methanol or preferably isopropanol.
Uit praktisch oogpunt worden de reacties bij voorkeurin een stap uitgevoerd door de oplossingen van de uitgangsstoffenmet elkaar te mengen bij de kooktemperatuur van het gekozen oplos¬middel. Wanneer de reactie voltooid is, wordt het na afkoelen verkregenprodukt gefiltreerd en daarna gekristalliseerd uit water met zeergoede opbrengsten (84-87%). Door de toepassing van de werkwijzeen van de reactieomstandigheden volgens de uitvinding kan ook deracemische vorm van dropropizine met betere opbrengsten wordenverkregen in vergelijking met de werkwijze van het bovengenoemdeBritse octrooischrift.From a practical point of view, the reactions are preferably carried out in one step by mixing the solutions of the starting materials together at the boiling temperature of the selected solvent. When the reaction is complete, the product obtained after cooling is filtered and then crystallized from water with very good yields (84-87%). The use of the reaction conditions processes according to the invention also allows the racemic form of dropropizine to be obtained in better yields compared to the process of the above-mentioned British Patent.
De werkwijze volgens de uitvinding heeft dan ook hetvoordeel, in vergelijking met de bekende werkwijzen, dat dezezonder problemen kan worden uitgevoerd, specifiek en selectiefis en betere opbrengsten geeft. Een ander positief aspect vande nieuwe werkwijze is de kristallisatie uit water van linksdraaienden rechtsdraaiend dropropizine , waarbij produkten worden verkregenmet een zeer goede zuiverheidsgraad . Dit is een voordeel omdatdeze verbindingen op farmaceutisch gebied worden gebruikt.The method according to the invention therefore has the advantage, compared to the known methods, that it can be carried out without problems, is specific and selective and gives better yields. Another positive aspect of the new process is the crystallization from water of counterclockwise clockwise to clockwise dropropizine, whereby products with a very good degree of purity are obtained. This is an advantage because these compounds are used in the pharmaceutical field.
De uitvinding zal nu uitvoeriger worden toegelicht aande hand van voorbeelden.The invention will now be explained in more detail by means of examples.
Voorbeeld IExample I
Bereiding van linksdraaiend dropropizine [S(-)-3-(4-fenylpiperazin-l-yl)propaan-1,2-diol]Preparation of counterclockwise dropropizine [S (-) - 3- (4-phenylpiperazin-1-yl) propane-1,2-diol]
Aan een oplossing van 37 g (0,5 mol) (R)-glycidol in150 ml isopropanol wordt een oplossing van 81,1 g (0,5 mol) 1-fenylpiperazine in 100 ml isopropanol toegevoegd , waarbij de tem¬peratuur, beneden 30°C wordt gehouden. Daarna wordt de oplossing1 uur onder terugvloeiing gekookt; het mengsel wordt vervolgenstot 0°C afgekoeld , waarna men het gedurende de nacht laat staan.To a solution of 37 g (0.5 mol) (R) -glycidol in 150 ml isopropanol is added a solution of 81.1 g (0.5 mol) 1-phenylpiperazine in 100 ml isopropanol, the temperature being lower Is kept at 30 ° C. The solution is then refluxed for 1 hour; the mixture is then cooled to 0 ° C and left overnight.
Het produkt wordt afgefiltreerd en met 300 ml water gekristalliseerdonder verkrijging van 102,1 g (86,4%) [S(-)-3-(4-fenylpiperazin-1-yl)propaan-1,2-diol] met smeltpunt 104-105°C, [a]^5= -11° (c= 3%, EtOH).The product is filtered off and crystallized with 300 ml of water to obtain 102.1 g (86.4%) of [S (-) - 3- (4-phenylpiperazin-1-yl) propane-1,2-diol] melting point 104 -105 ° C, [α] D 25 = -11 ° (c = 3%, EtOH).
Analyse C13H20N2°2·Analysis C13H20N2 ° 2
Berekend Gevonden C 66,07% C 66,04% - 0,03 H 8,53% H 8,58% + 0,05 N 11,85% N 12,01% + 0,16 0 13,54% O 13,37% - 0,17Calculated Found C 66.07% C 66.04% - 0.03 H 8.53% H 8.58% + 0.05 N 11.85% N 12.01% + 0.16 0 13.54% O 13.37% - 0.17
Onder toepassing van dezelfde methode maar met (S)-glycidolin plaats van (R)-glycidol wordt 101,4 g (85,9%) rechtsdraaienddropropizine verkregen met smeltpunt 104-105°C en [a]^= + 11° (c= 3%, EtOH).Using the same method but with (S) -glycidolin instead of (R) -glycidol, 101.4 g (85.9%) of right-turning dropropizine are obtained, mp 104-105 ° C and [a] ^ = + 11 ° (c = 3%, EtOH).
Voorbeeld IIExample II
Bereiding van racemisch dropropizine [(+)-3-(4-fenyl-piperazin-l-yl)propaan-l,2-diol]Preparation of racemic dropropizine [(+) - 3- (4-phenyl-piperazin-1-yl) propane-1,2-diol]
In 300 ml isopropanol wordt 74 g (1 mol) 2,3-epoxy-l-propanol opgelost. Aan deze oplossing wordt een oplossing van 162,2 g(1 mol) 1-fenylpiperazine in 200 ml isopropanol toegevoegd, waarbijmen de temperatuur vrijelijk laat oplopen, en daarna wordt het mengsel 1 uur onder terugvloeiing verhit. De reactieoplossing wordt vervolgenstot 0°C afgekoeld, waarna men deze gedurende de nacht laat staan.74 g (1 mol) of 2,3-epoxy-1-propanol are dissolved in 300 ml of isopropanol. To this solution, a solution of 162.2 g (1 mole) of 1-phenylpiperazine in 200 ml of isopropanol is added, allowing the temperature to rise freely, and then the mixture is refluxed for 1 hour. The reaction solution is then cooled to 0 ° C and left overnight.
De witte kristallen van het verkregen produkt worden afgefiltreerden met 600 ml water gekristalliseerd. Er wordt 200,4 g (84,8%) vanhet produkt verkregen met smeltpunt 103-105°C.The white crystals of the resulting product are filtered off with 600 ml of crystallized water. 200.4 g (84.8%) of the product are obtained, m.p. 103-105 ° C.
C13H20N2°2C13H20N2 ° 2
AnalyseAnalysis
Berekend Gevonden C 66,07% 66,02% - 0,05 H 8,53% 8,62% + 0,09 N 11,85% 11,98% + 0,13 0 13,54% 13,38% - 0,16Calculated Found C 66.07% 66.02% - 0.05 H 8.53% 8.62% + 0.09 N 11.85% 11.98% + 0.13 0 13.54% 13.38% - 0.16
Claims (4)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2161188 | 1988-08-01 | ||
| IT8821611A IT1226570B (en) | 1988-08-01 | 1988-08-01 | LEVO- AND RIGHT-DROPROPIZINE PREPARATION PROCEDURE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NL8901701A true NL8901701A (en) | 1990-03-01 |
Family
ID=11184306
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NL8901701A NL8901701A (en) | 1988-08-01 | 1989-07-04 | PROCESS FOR THE PREPARATION OF LEFT-ROTATING AND RIGHT-ROTATING DROPROPIZINE. |
Country Status (5)
| Country | Link |
|---|---|
| ES (1) | ES2014187A6 (en) |
| FR (1) | FR2634765B1 (en) |
| IT (1) | IT1226570B (en) |
| LU (1) | LU87538A1 (en) |
| NL (1) | NL8901701A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1231158B (en) * | 1989-07-20 | 1991-11-19 | Dompe Farmaceutici Spa | PROCEDURE FOR THE OPTICAL RESOLUTION OF DRUG. |
| IT1254452B (en) * | 1992-02-14 | 1995-09-25 | Dompe Farmaceutici Spa | N-OXIDES AND N, N'-DIOXIDES OF 3- (PIPERAZIN-1-IL) -PROPAN-1,2-DIOLS |
| IT1254993B (en) * | 1992-06-24 | 1995-10-11 | PROCEDURE FOR THE PREPARATION OF THE ENANTIOMERS OF DROPROPIZINE | |
| IT1318650B1 (en) * | 2000-07-28 | 2003-08-27 | Dompe Spa | 1,3-DIOSSOLANS WITH ANTI-TOXIC ACTIVITY. |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB938646A (en) * | 1961-03-16 | 1963-10-02 | Henri Morren | New piperazine derivatives |
| IT1203721B (en) * | 1983-12-29 | 1989-02-23 | Dompe Farmaceutici Spa | OPTICALLY ACTIVE COMPOUNDS WITH ANTITOSSE AND CENTRAL SEDATIVE ACTIVITIES, PROCEDURE FOR PREPARATION AND COMPOSITIONS CONTAINING THEM |
| NL8801622A (en) * | 1988-06-25 | 1990-01-16 | Stamicarbon | PREPARATION OF ENANTIOMERS OF DROPROPIZINE. |
-
1988
- 1988-08-01 IT IT8821611A patent/IT1226570B/en active
-
1989
- 1989-05-18 FR FR8906484A patent/FR2634765B1/en not_active Expired - Lifetime
- 1989-06-14 LU LU87538A patent/LU87538A1/en unknown
- 1989-07-04 NL NL8901701A patent/NL8901701A/en not_active Application Discontinuation
- 1989-07-31 ES ES8902707A patent/ES2014187A6/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| IT8821611A0 (en) | 1988-08-01 |
| IT1226570B (en) | 1991-01-24 |
| ES2014187A6 (en) | 1990-06-16 |
| FR2634765B1 (en) | 1994-05-27 |
| LU87538A1 (en) | 1991-02-18 |
| FR2634765A1 (en) | 1990-02-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| BV | The patent application has lapsed |