CN104628681A - Method for preparing beta-diketone c-nucleoside - Google Patents
Method for preparing beta-diketone c-nucleoside Download PDFInfo
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- CN104628681A CN104628681A CN201510042836.2A CN201510042836A CN104628681A CN 104628681 A CN104628681 A CN 104628681A CN 201510042836 A CN201510042836 A CN 201510042836A CN 104628681 A CN104628681 A CN 104628681A
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D307/18—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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Abstract
The invention discloses a method for preparing c-nucleoside. The method comprises the following steps: carbohydrate 1 with exposed anomer hydroxyl and alkynone 2 conduct a Michael addition reaction; and the addition product 3 is subjected to O-C rearrangement under the catalysis of Lewis acid to generate a beta-diketone c-nucleoside compound 4. According to the method, the O-C rearrangement reaction under the catalysis of Lewis acid is applied to the synthesis of beta-diketone c-nucleoside for the first time, the efficiency is high, the conditions are mild, and the operation is easy, thereby laying a firm foundation for effective synthesis of various heterocyclic c-nucleosides with patent medicine activity.
Description
Technical field
The present invention relates to carbon glycoside synthesis technical field, particularly a kind of method preparing beta-diketon class carbon nucleosides.
Background technology
Nucleosides is the main component of nucleic acid; also be the very important small molecules of a class; participate in the reservation of gene information in organism, copy and transcribe; and this also just nucleoside medicine can effectively control and treat major cause [(a) Otov á, the B. of the persistent ailments such as acquired immune deficiency syndrome (AIDS) (AIDS), hepatitis B; Hrdy, J.; Votruba, I.; Holy, A. Anticancer Res. 2009,29,1295. (b) De Clercq, E. Med. Res. Rev. 2009,29,571.].
Non-natural nucleoside and Nucleotide are similar because its chemical structure and natural nucleus glycoside and Nucleotide have in various degree, so can mix the spurious with the genuine in vivo, can play interference or directly act on the effect of metabolic process of nucleic acid.Therefore these compounds have very important status in antiviral and antineoplastic chemotherapy medicine.
Carbon nucleosides is the compound that heterocycle is connected by C-C key with glycosyl.This C-nucleosides gets up compared with N-nucleosides, has stronger biological and chemical stability, as [Yao Qizheng, nucleosides chemosynthesis, 2005] such as resistance to acid hydrolysis and enzymolysis.Because some carbon nucleosides has the antiviral of highly significant and antitumour activity, therefore people get more and more to its research in recent years.And the carbon nucleoside compound that different head position connects beta-diketon class is the extraordinary precursor of one synthesizing carbon nucleosides heterocycle, it can synthesize various heterocyclic C-nucleosides efficiently with hydrazine hydrate and hydration azanol.But up to the present, for its synthetic method actually rare.And the invention provides a kind of method of carbon nucleoside compound of good synthesis beta-diketon class.
Summary of the invention:
The object of this invention is to provide a kind of method effectively preparing beta-diketon class carbon nucleoside compound.
The present invention is achieved by the following measures:
A kind of method preparing beta-diketon class carbon nucleosides, the method is utilize the sugar 1 that different head position hydroxyl is exposed, with acetylenic ketone 2, Michael addition reaction occurs, obtained adduct aryl enol ether 3, then adduct aryl enol ether 3 is again under the catalysis of Lewis acid, reset through O → C and generate beta-diketon class carbon nucleoside compound 4, instead
process is:
Wherein, R1 is the β-D-Glucose base of full guard, the alpha-D-glucose base of full guard, β-D-the galactosyl of full guard, α-D-the galactosyl of full guard, β-D-MANNOSE the base of full guard, α-D-MANNOSE the base of full guard, β-D-the xylosyl of full guard, the alpha-D-xylose base of full guard, β-D-2-aminoglucose the glycosyl of full guard, α-D-2-aminoglucose the glycosyl of full guard, α-L-the rhamanopyranosyl of full guard, β-L-the rhamanopyranosyl of full guard, α-D-R the base of full guard, β-D-R the base of full guard, α-L-arabinose the base of full guard, β-L-arabinose the base of full guard, α-L-fucose the base of full guard, β-L-fucose the base of full guard, β-D-Glucose aldehydic acid the base of full guard, the alpha-D-glucose aldehydic acid base of full guard, β-D-galacturonic the acidic group of full guard, or the α-D-galacturonic acidic group of full guard, protecting group wherein on sugar is ethanoyl, benzoyl or benzyl,
R2, R3 represent do not replace, monosubstituted, two replace, three replace or four to replace, R2 and R3 is one or more in H, F, Cl, Br, I, amino, the amino of replacement, N3, guanidine radicals, the saturated alkyl of CN, C1-C8, the saturated alkoxyl group of C1-C8, C1-C8 cycloalkyl, C1-C8 thiazolinyl and C1-C8 alkynyl.
In the present invention, the described method preparing adduct aryl enol ether and condition can be ordinary method and the condition of the similar addition reaction in this area, the present invention is following method and condition particularly preferably: in organic solvent, under the effect of catalyzer, sugar exposed for different head position hydroxyl and acetylenic ketone are carried out addition reaction; The consumption of described catalyzer is 0.1 times of the molar weight of the sugar that different head position hydroxyl is exposed; Described temperature of reaction is 25 DEG C, and the reaction times is 1 to 24 hours.
The described rearrangement reaction preparing beta-diketon class carbon nucleoside compound comprises the following step: in organic solvent, under protection of inert gas, under the existence of siccative, under lewis acidic catalysis and alkali effect, compound aryl enol ether is made to carry out rearrangement reaction; The consumption of described lewis acid catalyst is 0.05 times of the molar weight of the sugar that different head position hydroxyl is exposed, and the consumption of alkali is 0.1 ~ 3 times of the molar weight of the sugar that different head position hydroxyl is exposed, and better is 1.2 times; Described temperature of reaction-30 DEG C is to 25 DEG C, and the reaction times is 0.1 to 24 hours; The consumption of described siccative is 1.0 ~ 4.0 times of the molar weight of aryl enol ether.
It is described that to prepare catalyzer used in adduct aryl enol ether be DMAP, DBU;
The described Lewis acid prepared used by beta-diketon class carbon nucleoside compound is: one or more in Bi (OTf) 3, PPh3Au (NTf) 2, Hf (OTf) 3, La (OTf) 3, Sm (OTf) 3, Yb (OTf) 3, Zn (OTf) 2, HfCl3, In (OTf) 3, Sc (OTf) 3.
Wherein, described organic solvent can be this area Conventional solvents used, as one or more in methylene dichloride, toluene, Nitromethane 99Min. and acetonitrile.The preferred methylene dichloride of the present invention.
Described rare gas element is preferably dry rare gas element, as high-purity argon gas and/or high pure nitrogen.
It is described that to prepare catalyzer used in aryl enol ether be DMAP, DBU;
Described siccative is preferably one or more in 3 molecular sieves, 4 molecular sieves, 5 molecular sieves, 3 molecular sieves of pickling, 4 molecular sieves of pickling, 5 molecular sieves of pickling, anhydrous sodium sulphate, anhydrous calciumsulphate, anhydrous cupric sulfate and anhydrous magnesium sulfate.The consumption of siccative is preferably 1.0 ~ 4.0 times of the molar weight of compound 3, and better is 2.0 times.
Described alkali is one or more in K2CO3, DBU, DTBMP.
Technique effect of the present invention is: the O → C rearrangement reaction under Louis acid catalysis is applied in the synthesis of beta-diketon class carbon nucleosides by the method first, efficiency is high, mild condition and easy handling, for synthesizing the various heterocyclic carbon nucleosides with patent medicine activity has efficiently established solid basis in the future.
Embodiment
By following examples, specific implementation method of the present invention is described, but this embodiment is not for limiting the scope of the invention.
Embodiment 1
The preparation of 1-(2,3,5-tri--O-benzyl-alpha-D-ribose)-1,3-diphenyl propane-1,3-diketone
Step 1
The preparation of (3S, 5R)-3,4-bis-(benzyloxy)-5-((benzyloxy) methyl) tetrahydrofuran (THF)-2-alcohol
Taking 12 g(73.1 mmol) ribose methylglucoside is in 250 mL eggplant type bottles, add 160 mL analytical pure DMF, slowly 38 mL BnBr are instilled after adding 17 g NaH under ice bath, slowly rise to room temperature, reaction is spent the night, TLC tracks to reaction to be terminated, slowly add after methyl alcohol extracts reaction of going out and extract with EA, water washing, thick product pillar layer separation (PE:EA=15:1 → 9:1) obtains compound (2R, 4S)-3,4-bis-(benzyloxy)-2-((benzyloxy) methyl)-5-methoxyl group tetrahydrofuran (THF) (28.6 g, 65.8 mmol, 90%).
Weigh Compound 38a (3.5g, 8.0 mmol) in 100 mL eggplant type bottles, add 28 mL 1,4-dioxane adds 28 mL 4 N HCl after making it dissolving, temperature rising reflux reacts 3 h, TLC tracks to reaction to be terminated rear EA and extracts, water washing, again successively with saturated NaHCO3 solution and the washing of saturated NaCl solution, after concentrating under reduced pressure, thick product pillar layer separation (PE:EA=5:1 → 3.5:1) obtains product (3S, 5R)-3,4-bis-(benzyloxy)-5-((benzyloxy) methyl) tetrahydrofuran (THF)-2-alcohol (2.9 g, 6.9 mmol, 86%).
Step 2
3-(((3S, 5R)-3,4-bis-(benzyloxy)-5-((benzyloxy) methyl) tetrahydrofuran (THF)-2-replaces) oxo)-1,3-diphenylpropyl-2-alkene-1-ketone
Take the exposed glycosyl (3S in 1.15 mmol different head position, 5R)-3, 4-bis-(benzyloxy)-5-((benzyloxy) methyl) tetrahydrofuran (THF)-2-alcohol is in the eggplant type bottle of 25 mL dryings, add 1.38 mmol(1.2 eq) 1, 3-diphenylpropyl-2-alkynes-1-ketone and 0.12 mmol(0.1 eq) DMAP, add the DCM of 5 mL dryings, argon shield, room temperature reaction, TLC tracks to reaction to be terminated, after the direct concentrating under reduced pressure of reaction solution, pillar layer separation obtains compound 3-(((3S, 5R)-3, 4-bis-(benzyloxy)-5-((benzyloxy) methyl) tetrahydrofuran (THF)-2-replaces) oxo)-1, 3-diphenylpropyl-2-alkene-1-ketone.
Step 3
The synthesis of 1-(2,3,5-tri--O-benzyl-alpha-D-ribose)-1,3-diphenyl propane-1,3-diketone
Take above-mentioned adduct 0.15 mmol; add 25 mg(1.2 eq) K2CO3 powder; appropriate 4 MS; and 2 Nitromethane 99Min.s of mL drying; under argon shield, dry ice acetone bath adds 4 mg Sc (OTf) 3 after-30 DEG C; make it slowly rise to room temperature reaction, TLC tracks to reaction to be terminated.The saturated NaHCO3 extraction of reaction solution is gone out, and EA extracts, and water washing, thick product pillar layer separation obtains compound 1-(2,3,5-tri--O-benzyl-alpha-D-ribose)-1,3-diphenyl propane-1,3-diketone (α, productive rate: 74%).
(PhMe:EA = 24:1); [α] D 25 = +186.7 (c 1.0, CHCl3); 1H NMR (300 MHz, CDCl3) δ 8.06 (d, J = 8.1 Hz, 2 H), 7.79 (d, J = 7.5 Hz, 2 H), 7.53-6.96 (m, 21 H), 6.25(d, J = 9.9 Hz, 1 H), 5.31 (dd, J = 5.1, 9.9 Hz, 1 H), 4.72-4.59 (m, 3 H), 4.46-4.24 (m, 4 H), 4.26 (dd, J = 4.2, 7.1 Hz, 1 H), 4.12 (t, J = 4.5 Hz, 1 H), 3.45 (d, J = 3.9 Hz, 1 H); 13C NMR (100 MHz, CDCl3 ) δ194.8, 193.1, 138.0, 137.8, 137.6, 137.4, 136.7, 133.1, 132.8, 129.2, 129.0, 128.5, 128.4, 128.3, 128.2, 128.1, 127.94, 127.87, 127.84, 127.77, 127.50, 127.47, 127.38, 127.36, 81.4, 80.7, 79.9, 78.3, 77.3, 77.0, 76.7, 73.5, 73.2, 73.0, 70.1, 56.6; HRMS (ESI) calcd for C41H38O6Na+: 649.2561, Found: 649.2560.
Embodiment 2
The synthesis of 1-(2,3,5-tri--O-benzyl-alpha-D-ribose)-1,3-bis-p-methylphenyl propane-1,3-diketone
Synthetic method is (α, productive rate 52%) as described in Example 1:
(PhMe:EA = 24:1); [α] D 25 = +179.3 (c 1.0, CHCl3); 1H NMR (400 MHz, CDCl3) δ 7.89 (d, J =8.0 Hz, 2 H), 7.62 (dd, J =8.4 Hz, 2 H), 7.28-6.89 (m, 19 H), 6.08 (d, J =10.0 Hz, 2 H), 5.17 (dd, J = 4.8, 10.0 Hz, 1 H), 4.63-4.52 (m, 3 H), 4.35-4.21 (m, 4 H), 4.17 (dd, J = 4.0, 9.2 Hz, 1 H), 4.02 (t, J = 4.8 Hz, 1 H), 3.38 (dt, J =9.2, 11.2 Hz, 2 H), 2.27 (s, 3 H), 2.22 (s, 3 H); 13C NMR (400 MHz, CDCl3 ) δ193.5, 192.0, 143.0, 142.7, 137.2, 137.0, 136.8, 134.0, 133.3, 128.4, 128.2, 128.1, 127.7, 127.4, 127.3, 127.0, 126.9, 126.54, 126.46, 126.3, 80.4, 79.5, 79.1, 77.2, 76.4, 76.0, 72.6, 72.3, 71.9, 69.1, 55.4, 20.6, 20.5; HRMS (ESI) calcd for C43H42O6Na+: 677.2874, Found: 677.2858。
Embodiment 3
The synthesis of 1-(2,3,5-tri--O-benzyl-alpha-D-ribose)-1,3-di-p-methoxy phenyl-propane-1,3-diketone
Synthetic method is (α, productive rate 46%) as described in Example 1:
(PhMe:EA = 24:1); [α] D 25 = +189.4 (c 1.3, CHCl3), 1H NMR (400 MHz, CDCl3) δ 7.98 (d, J =8.8 Hz, 2 H), 7.71 (d, J =8.8 Hz, 2 H), 7.28-6.91 (m, 15 H), 6.78 (d, J =8.4 Hz, 2 H), 6.63 (d, J = 8.8 Hz, 2 H), 6.00 (d, J = 9.6 Hz, 1 H), 5.16 (dd, J = 4.8, 10.0 Hz, 1 H), 4.64-4.52 (m, 3 H), 4.37-4.22 (m, 4 H), 4.18 (dd, J = 4.0, 8.8 Hz, 1 H), 4.03 (t, J = 4.8 Hz, 1 H), 3.74 (s, 3H), 3.71 (s, 3H), 3.43-3.35 (m, 2H); 13C NMR (400 MHz, CDCl3 ) δ193.4, 192.0, 163.6, 163.3, 138.2, 137.9, 137.8, 131.6, 130.8, 130.6, 129.8, 128.4, 128.3, 128.0, 127.9, 127.8, 127.54, 127.46, 127.3, 113.7, 113.6, 81.2, 80.5, 80.2, 78.3, 77.3, 77.0, 76.7, 73.6, 73.3, 72.9, 70.2, 56.1, 55.4; HRMS (ESI) calcd for C43H42O8Na+: 709.2772, Found: 709.2771.
Embodiment 4
The synthesis of 1-(2,3,5-tri--O-benzyl-alpha-D-ribose)-1,3-bis-pair of fluorophenyl propane-1,3-diketone
Synthetic method is (α, productive rate 63%) as described in Example 1:
(PhMe:EA = 24:1); [α] D 25 = +165.5 (c 1.0, CHCl3), 1H NMR (300 MHz, CDCl3) δ 7.98 (dd, J =3.9, 6.6 Hz, 2 H), 7.67 (dd, J = 3.9, 6.6 Hz, 2 H), 7.29-6.89 (m, 17 H), 6.78 (t, J = 6.6 Hz, 2 H), 6.07 (d, J = 7.5 Hz, 1 H), 5.22 (dd, J = 4.2, 7.2 Hz, 1 H), 4.63-4.49 (m, 3 H), 4.39-4.21 (m, 4 H), 4.17 (dd, J = 3.0, 6.3 Hz, 1 H), 4.04 (t, J = 3.3 Hz, 1 H), 3.37 (dd, J =0.9, 3.0 Hz, 1 H); 13C NMR (400 MHz, CDCl3 ) δ193.0, 191.3, 167.1, 166.8, 164.6, 164.2, 138.0, 137.8, 137.4, 131.9, 131.8, 131.1, 131.0, 128.5, 128.3, 128.1, 128.0, 127.96, 127.8, 127.6, 127.5, 115.8, 115.5, 115.3, 81.2, 81.0, 79.9, 78.5, 77.3, 77.0, 76.7, 73.5, 73.4, 73.1, 70.2, 56.6; HRMS (ESI) calcd for C41H36F2O6Na+: 685.2372, Found: 685.2371.
Embodiment 5
The synthesis of 1-(2,3,4-tri--O-benzyl-alpha-L-rhamnosyl)-1,3-bis-(4-fluorophenyl) phenylpropyl alcohol alkane-1,3-diketone
Synthetic method is (β, productive rate 43%) as described in Example 1:
(PhMe:EA = 24:1); [α] D 25 = -36.9 (c 1.0, CHCl3); 1H NMR (300 MHz, CDCl3) δ 8.02 (dd, J =5.4, 7.2 Hz, 2 H), 7.92 (dd, J = 5.4, 9.0 Hz, 2 H), 7.99-7.00 (m, 19 H), 5.39-5.29 (m, 2 H), 4.73-4.32 (m, 6 H), 3.80-3.73 (m, 3 H), 3.58 (t, J = 6.6 Hz, 1 H), 1.21 (d, J = 6.3 Hz, 3H); 13C NMR (100 MHz, CDCl3 ) δ 191.8, 191.1, 167.0, 164.6, 164.5, 138.2, 138.0, 137.8, 133.4, 133.0, 131.5, 131.4, 128.4, 128.3, 128.1, 128.0, 127.9, 127.8, 127.7, 127.6, 127.5, 115.98, 115.95, 115.8, 115.7, 79.1, 77.3, 77.0, 76.7, 76.3, 75.4, 73.9, 72.4, 72.0, 71.5, 71.0, 60.6, 17.3; HRMS (ESI) calcd for C42H38O6F2Na+: 699.2529, Found: 699.2522。
Claims (10)
1. prepare the method for beta-diketon class carbon nucleosides for one kind, it is characterized in that the method is utilize the sugar 1 that different head position hydroxyl is exposed, with acetylenic ketone 2, Michael addition reaction occurs, obtained adduct aryl enol ether 3, then adduct aryl enol ether 3 is again under the catalysis of Lewis acid, reset through O → C and generate beta-diketon class carbon nucleoside compound 4, reaction process is:
Wherein, R
1it is the β-D-Glucose base of full guard, the alpha-D-glucose base of full guard, β-D-the galactosyl of full guard, α-D-the galactosyl of full guard, β-D-MANNOSE the base of full guard, α-D-MANNOSE the base of full guard, β-D-the xylosyl of full guard, the alpha-D-xylose base of full guard, β-D-2-aminoglucose the glycosyl of full guard, α-D-2-aminoglucose the glycosyl of full guard, α-L-the rhamanopyranosyl of full guard, β-L-the rhamanopyranosyl of full guard, α-D-R the base of full guard, β-D-R the base of full guard, α-L-arabinose the base of full guard, β-L-arabinose the base of full guard, α-L-fucose the base of full guard, β-L-fucose the base of full guard, β-D-Glucose aldehydic acid the base of full guard, the alpha-D-glucose aldehydic acid base of full guard, β-D-galacturonic the acidic group of full guard, or the α-D-galacturonic acidic group of full guard, protecting group wherein on sugar is ethanoyl, benzoyl or benzyl, R
2, R
3represent do not replace, monosubstituted, two replace, three replace or four replace, R
2and R
3for amino, the N of H, F, Cl, Br, I, amino, replacement
3, guanidine radicals, CN, C
1-C
8saturated alkyl, C
1-C
8saturated alkoxyl group, C
1-C
8cycloalkyl, C
1-C
8thiazolinyl and C
1-C
8one or more in alkynyl.
2. a kind of method preparing beta-diketon class carbon nucleosides described in 1 is required according to right, it is characterized in that: the described method preparing adduct aryl enol ether and condition can be ordinary method and the condition of the similar addition reaction in this area, the present invention is following method and condition particularly preferably: in organic solvent, under the effect of catalyzer, sugar exposed for different head position hydroxyl and acetylenic ketone are carried out addition reaction; The consumption of described catalyzer is 0.1 times of the molar weight of the sugar that different head position hydroxyl is exposed; Described temperature of reaction is 25 DEG C, and the reaction times is 1 to 24 hours.
3. a kind of method preparing beta-diketon class carbon nucleosides described in 1 is required according to right, it is characterized in that: the described rearrangement reaction preparing beta-diketon class carbon nucleoside compound comprises the following step: in organic solvent, under protection of inert gas, under the existence of siccative, under lewis acidic catalysis and alkali effect, compound aryl enol ether is made to carry out rearrangement reaction; The consumption of described lewis acid catalyst is 0.05 times of the molar weight of the sugar that different head position hydroxyl is exposed, and the consumption of alkali is 0.1 ~ 3 times of the molar weight of the sugar that different head position hydroxyl is exposed, and better is 1.2 times; Described temperature of reaction-30 DEG C is to 25 DEG C, and the reaction times is 0.1 to 24 hours; The consumption of described siccative is 1.0 ~ 4.0 times of the molar weight of aryl enol ether.
4. require a kind of method preparing beta-diketon class carbon nucleosides described in 2 according to right, it is characterized in that: described to prepare catalyzer used in adduct aryl enol ether be DMAP, DBU.
5. require a kind of method preparing beta-diketon class carbon nucleosides described in 3 according to right, to it is characterized in that: the described Lewis acid prepared used by beta-diketon class carbon nucleoside compound is: Bi (OTf)
3, PPh
3au (NTf)
2, Hf (OTf)
3, La (OTf)
3, Sm (OTf)
3, Yb (OTf)
3, Zn (OTf)
2, HfCl
3, In (OTf)
3, Sc (OTf)
3in one or more.
6. a kind of method preparing beta-diketon class carbon nucleosides described in 2,3 is required according to right, it is characterized in that: described organic solvent can be this area Conventional solvents used, as one or more in methylene dichloride, toluene, Nitromethane 99Min. and acetonitrile, the preferred methylene dichloride of the present invention.
7. require a kind of method preparing beta-diketon class carbon nucleosides described in 3 according to right, it is characterized in that: described rare gas element is preferably dry rare gas element, as high-purity argon gas and/or high pure nitrogen.
8. require a kind of method preparing beta-diketon class carbon nucleosides described in 2 according to right, it is characterized in that: described to prepare catalyzer used in aryl enol ether be DMAP, DBU.
9. a kind of method preparing beta-diketon class carbon nucleosides described in 3 is required according to right, it is characterized in that: described siccative is preferably one or more in 3 molecular sieves, 4 molecular sieves, 5 molecular sieves, 3 molecular sieves of pickling, 4 molecular sieves of pickling, 5 molecular sieves of pickling, anhydrous sodium sulphate, anhydrous calciumsulphate, anhydrous cupric sulfate and anhydrous magnesium sulfate
The consumption of siccative is preferably 1.0 ~ 4.0 times of the molar weight of compound 3, and better is 2.0 times.
10. require a kind of method preparing beta-diketon class carbon nucleosides described in 3 according to right, it is characterized in that: described alkali is preferably K
2cO
3, one or more in DBU, DTBMP.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000071785A2 (en) * | 1999-05-20 | 2000-11-30 | Zeneca Limited | 2-cylcoalkylcarbonylcyclohexane-1,3-dione derivatives as herbicides |
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|---|---|---|---|---|
| WO2000071785A2 (en) * | 1999-05-20 | 2000-11-30 | Zeneca Limited | 2-cylcoalkylcarbonylcyclohexane-1,3-dione derivatives as herbicides |
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