DD277683A1 - PROCESS FOR PRODUCING BRANCHED SUGAR - Google Patents
PROCESS FOR PRODUCING BRANCHED SUGAR Download PDFInfo
- Publication number
- DD277683A1 DD277683A1 DD32273488A DD32273488A DD277683A1 DD 277683 A1 DD277683 A1 DD 277683A1 DD 32273488 A DD32273488 A DD 32273488A DD 32273488 A DD32273488 A DD 32273488A DD 277683 A1 DD277683 A1 DD 277683A1
- Authority
- DD
- German Democratic Republic
- Prior art keywords
- methyl
- erythro
- benzylidene
- hexopyranoside
- preparation
- Prior art date
Links
- 235000000346 sugar Nutrition 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 150000008163 sugars Chemical class 0.000 claims abstract description 6
- 239000002168 alkylating agent Substances 0.000 claims abstract description 4
- 229940100198 alkylating agent Drugs 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 abstract description 12
- 125000004414 alkyl thio group Chemical group 0.000 abstract description 4
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- -1 (methylthio) methylene Chemical group 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 102100029368 Cytochrome P450 2C18 Human genes 0.000 description 1
- 101000919360 Homo sapiens Cytochrome P450 2C18 Proteins 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 125000004705 ethylthio group Chemical group C(C)S* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Saccharide Compounds (AREA)
Abstract
Die Erfindung betrifft ein Verfahren zur Herstellung von verzweigten Zuckern. Ziel der Erfindung ist es, ein Verfahren fuer die Herstellung von Methyl-3-&bis(alkylthio)methylen!-4,6-0-benzyliden-3-desoxy-a,D-erythro-hexopyranosid-2-ulosen zu entwickeln. Erfindungsgemaess koennen die verzweigten Zucker der allgemeinen Formel III, in der R fuer einen Alkyl-, Aralkyl- bzw. Hetaralkylrest steht, durch Umsetzung der Methyl-4,6-0-benzyliden-3-desoxy-a,D-erythro-hexopyranosid-2-ulose I mit Schwefelkohlenstoff und Alkylierungsmitteln der allgemeinen Formel II, in der R die obige Bedeutung besitzt und X fuer ein Halogenatom steht, in Gegenwart von Basen hergestellt werden. Diese verzweigten Zucker koennen als organische Zwischenprodukte fuer weitere Synthesen verwendet werden. Sie sind insbesondere zur Herstellung von potentiellen Pharmazeutica geeignet.The invention relates to a process for the preparation of branched sugars. The aim of the invention is to develop a process for the preparation of methyl-3- & bis (alkylthio) methylene! -4,6-0-benzylidene-3-deoxy-a, D-erythro-hexopyranoside-2-uloses. According to the invention, the branched sugars of the general formula III in which R is an alkyl, aralkyl or heteroalkyl radical can be prepared by reacting the methyl-4,6-O-benzylidene-3-deoxy-a, D-erythro-hexopyranoside 2-ulose I with carbon disulfide and alkylating agents of general formula II in which R has the above meaning and X is a halogen atom, are prepared in the presence of bases. These branched sugars can be used as organic intermediates for further syntheses. They are particularly suitable for the preparation of potential Pharmazeutica.
Description
Die Erfindung betrifft ein Verfahren zur Herstellung von Methyl-3-[bis(alkylthio)methylen]-4,6-0-benzyliden-3-desoxy-a,D-erythro-hexopyranosid-2-ulosen. Diese verzeigten Zucker können als organische Zwischenprodukte für weitere Synthesen verwendet werden. Sie sind insbesondere zur Herstellung von potentiellen Pharmazeutica geeignet.The invention relates to a process for the preparation of methyl 3- [bis (alkylthio) methylene] -4,6-0-benzylidene-3-deoxy-a, D-erythro-hexopyranoside-2-uloses. These sugars can be used as organic intermediates for further syntheses. They are particularly suitable for the preparation of potential Pharmazeutica.
Methyl-3-(bis(alkylthio)methylenl-4,6-0-benzyliden-3-desoxy-a,D-erythro-hexopyranosid-2-ulosen sind bisher noch nicht bekannt.Methyl 3- (bis (alkylthio) methylene-4,6-O-benzylidene-3-deoxy-a, D-erythro-hexopyranoside-2-uloses are not yet known.
Ziel der Erfindung ist die Entwicklung eines Verfahrens zur Herstellung pharmazeutischer Wirkstoffe.The aim of the invention is the development of a process for the preparation of pharmaceutical active ingredients.
Aufgäbe der Erfindung ist es, i'uf der Basis der Methyl-4,6-0-benzyliden-3-desoxy-a,D-erythro-hexopyranosid-2-ulose eine Synthese der Methyl-3-|bis(alkylthio)methylen|-4,6-0-benzyliden-3-desoxy-a,D-erythro-hexopyranosid-2-ulosen zu ermöglichen.The object of the invention is, on the basis of methyl-4,6-O-benzylidene-3-deoxy-a, D-erythro-hexopyranoside-2-ulose, a synthesis of methyl-3- (bis (alkylthio) methyls 4,6-O-benzylidene-3-deoxy-a, D-erythro-hexopyranoside-2-ulose.
Erfindungsgemäß können die verzweigten Zucker der allgemeinen Formel II, in der R für einen Alkyl-, Aralkyl- bzw. Hetaralkylrest steht, durch Umsetzung der Methyl-4,6-0-benzyliden-3-desoxy-a,D-erythro-hexopyranosid-2-ulose I mit Schwefelkohlenstoff und Alkylierungsmitteln der allgemeinen Formel II, in der R die obige Bedeutung besitzt und X für ein Halogenatom steht, in Gegenwart von Basen hergestellt werden.According to the invention, the branched sugars of the general formula II in which R is an alkyl, aralkyl or heteroalkyl radical can be prepared by reacting the methyl-4,6-O-benzylidene-3-deoxy-a, D-erythro-hexopyranoside 2-ulose I with carbon disulfide and alkylating agents of general formula II in which R has the above meaning and X is a halogen atom, are prepared in the presence of bases.
Die Umsetzungen werden in wasserfreien organischen Lösungsmitteln, vorzugswesie in aprotischen mit Wasser mischbaren Lösungsmitteln, vorgenommen. Das Molverhältnis Hexopyranosidulose I und Base, vorzugsweise Natriumhydrid, beträgt 1:2. Schwefelkohlenstoff und die Alkylierungsmittel Il werden im Überschuß eingesetzt. Die Reaktionsmischungen sollten gerührt werden. Die Reaktionstemperaturen liegen um 2O0C. Die Reaktionszeiten betragen 30 Minuten bis zu drei Stunden. Durch Versetzen mit Wasser erfolgt die Ausfällung der Rohprodukte. Diese können nach dem Abfiltrieren und Wascher · it Wasser durch Umkristallisieren aus organischen Lösungsmitteln weiter gereinigt werden.The reactions are carried out in anhydrous organic solvents, preferably in aprotic water-miscible solvents. The molar ratio of hexopyranosidulose I and base, preferably sodium hydride, is 1: 2. Carbon disulfide and the alkylating agents II are used in excess. The reaction mixtures should be stirred. The reaction temperatures are around 2O 0 C. The reaction times are 30 minutes to three hours. By adding water, the precipitation of the crude products takes place. After filtration and washing with water, these can be further purified by recrystallization from organic solvents.
Methyl-4,6-0-benzyliden-3-[bis(methylthio)methylen)-3-desoxy-a,D-erythro-hexopyranosid-2-ulose Man suspendiert 0,01 mol/mol Natriumhydrid (eingesetzt als 80%kjc Suspension in Weißöl) in 10ml absolutem Dimethylformamid, vorsetzt die erhaltene Suspension unter Umrühren mit einer Mischung von 0,005mol/mol Methyl-4,6-0-benzyliden-3-desoxy-a,D-erythro-hexopyranosid-2-ulose, 0,01 mol/mol Schwefelkohlenstoff, 0,025mol/mol Methyliodid und 15ml Dimethylformamid, rührt 90 Minuten bei 22°C, gießt die Reaktionsmischung langsam unter Rühren in eine Mischung von 200 ml Eis/Wassor, filtriert den ausgefallenen Niederschlag ab, wäscht diesen mit Wasser und anschließend mit Petrolether und kristnllisiort ihn aus Methanol um.Methyl 4,6-O-benzylidene-3- [bis (methylthio) methylene) -3-desoxy-a, D-erythro-hexopyranoside-2-ulose. 0.01 mol / mol of sodium hydride (used as 80% kjc) is suspended Suspension in white oil) in 10 ml of absolute dimethylformamide, the resulting suspension is prepared with stirring with a mixture of 0.005 mol / mol of methyl-4,6-0-benzylidene-3-deoxy-a, D-erythro-hexopyranoside-2-ulose, 0 , 01 mol / mol carbon disulfide, 0.025 mol / mol of methyl iodide and 15 ml of dimethylformamide, stirred for 90 minutes at 22 ° C, the reaction mixture slowly poured into a mixture of 200 ml of ice / water with stirring, the precipitate filtered off, washed with water and then with petroleum ether and crystallized from methanol.
Ausbouto: 52% d. Th. Schmelzpunkt: 120-12215CIgOIbONaCIeIn)Exhaustion: 52% d. Th. Melting point: 120-122 15 CIgOIbONaCIeIn)
|aß°: 12,3 Mc = 1,03,CHCI3)a °: 12.3 Mc = 1.03, CHCl 3 )
C,,H2oO..,S2(368,5) Bor. C55.41 H5.47 S17.40C ,, H 2 oO .., S 2 (368.5) boron. C55.41 H5.47 S17.40
Gof. C55,20 H 5,30 S 17,21Gof. C55,20 H 5,30 S 17,21
Ausführungsbeispiel 2Embodiment 2
Methyl^6-0-benzyliden-3-desoxy-3-[bis(ethylthio)methylen]-a,D-erythro-hexopyranosid-2-ulose 0,005mol/mol Methyl^.e-O-benzyliden-S-desoxy-a.D-erythro-hexypyranosid^-ulose, 0,01 mol/mol Natriumhydrid, 0,01 mol/ mol Schwefelkohlenstoff und 0,025 mol/mol Ethyliodid werden umgesetzt, wie unter Ausführungsbeispiel 1 beschrieben. Man kristallisiert das Rohprodukt aus Cyclohexan um.Methyl ^ 6-O-benzylidene-3-deoxy-3- [bis (ethylthio) methylene] -α, D-erythro-hexopyranoside-2-ulose 0.005 mol / mol of methyl ^ .o-benzylidene-S-deoxy-aD- erythro-hexypyranoside-cellulose, 0.01 mol / mol of sodium hydride, 0.01 mol / mol of carbon disulfide and 0.025 mol / mol of ethyl iodide are reacted as described in Example 1. The crude product is recrystallized from cyclohexane.
Ausbeute: 63% d. Th. Schmelzpunkt: 115-117°C (gelbe Nadeln)Yield: 63% d. Th. Melting point: 115-117 ° C (yellow needles)
[α]έ°: -33,0° (c = 1,01,CHCI3)[α] έ °: -33.0 ° (c = 1.01, CHCl 3 )
C19H24O5S2(396,5) Ber. C57.55 H6.10 S 16,17C 19 H 24 O 5 S 2 (396.5) Ber. C57.55 H6.10 S 16,17
Gef. CE7.70 H 6,15 S 16,15Gef. CE7.70 H 6,15 S 16,15
1H-NMR (CPCI3): 1,07-1,30 2x CH3 (6H12x t), 2,80-3,12 2x CH2 (4H, 2x q), 3,47 CH3O (3H, s), 3,85-4,80 Protonen am Zuckergerüst (5H, m), 5,69 C6H5CH (1H, s), 7,27-7,50 Aromatenprotonen (5H, m) ppm. 1 H NMR (CPCI 3 ): 1.07-1.30 2x CH 3 (6H 1 2x t), 2.80-3.12 2x CH 2 (4H, 2x q), 3.47CH 3 O ( 3H, s), 3.85-4.80 protons on the sugar scaffold (5H, m), 5.69 C 6 H 5 CH (1H, s), 7.27-7.50 aromatic protons (5H, m) ppm.
74837483
OCHjOCHj
2NaM2NaM
2RX I-2Na+X -2H2 2RX I-2Na + X -2H 2
(RS)2C(RS) 2 C
OCHjOCHj
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD32273488A DD277683A1 (en) | 1988-12-07 | 1988-12-07 | PROCESS FOR PRODUCING BRANCHED SUGAR |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DD32273488A DD277683A1 (en) | 1988-12-07 | 1988-12-07 | PROCESS FOR PRODUCING BRANCHED SUGAR |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DD277683A1 true DD277683A1 (en) | 1990-04-11 |
Family
ID=5604694
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DD32273488A DD277683A1 (en) | 1988-12-07 | 1988-12-07 | PROCESS FOR PRODUCING BRANCHED SUGAR |
Country Status (1)
| Country | Link |
|---|---|
| DD (1) | DD277683A1 (en) |
-
1988
- 1988-12-07 DD DD32273488A patent/DD277683A1/en not_active IP Right Cessation
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| ENJ | Ceased due to non-payment of renewal fee |