CN1340550A - Process for preparing beta-6-dextran as high-activity oligose-type agricultural chemical - Google Patents
Process for preparing beta-6-dextran as high-activity oligose-type agricultural chemical Download PDFInfo
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Abstract
A process for synthesizing beta-6-dextran as high-activity oligose-type agricultural chemical uses glucose as initiating raw material, and includes such step as respectively synthesizing dextrose triose donor and receptor, under protection of TMSOTf using Schmidt glycosiding method to prepare protected 6-dextran with high output, and removing protecting radical to obtain beta-6-dextran. Its advantages are the simplified process, high yield and low cost.
Description
The invention belongs to field of biological pesticide, specifically provide the synthetic method of poly-six sugar in synthetic effectively high reactivity oligose-type agricultural chemical β-Portugal.
China is a large agricultural country, and because increasingly serious disease and pest threatens, the annual financial loss that causes because of diseases and pests of agronomic crop reaches tens billion of units, and country and peasant have all been caused serious loss.Therefore agricultural chemicals is seized of important status in agriculture production.But traditional toxicity of pesticide is very big, and life-time service can make insect develop immunity to drugs on the one hand and reduce drug effect, and what is more important tradition agricultural chemicals is very big with ecological pollution, destruction to human environment.Thereby the new trend that development is efficient, safe, eco-friendly novel agrochemical has become current pesticide developing.
The oligosaccharides biological pesticide is as the incitant of novel plant hormone of a class and plant resistance to environment stress reaction, and DEVELOPMENT PROSPECT has a wide range of applications in the crop growthing development and the prevention and control of plant diseases, pest control.Oligosaccharides can stimulating plant immune system response, produce the generation that active substance with disease resistance (as plant protecting chemical etc.) suppresses disease and pest.That oligose-type agricultural chemical has is efficient, free from environmental pollution, to advantages such as person poultry harmless, it is in the safe and efficient property of fruit, the vegetable disease control also characteristic of oligose-type agricultural chemical just, catered to the demand of people, thereby the research and development oligose-type agricultural chemical will have important significance for theories and very wide application prospect undoubtedly to green food.Recent two decades comes the CCRC (composite oligosaccharide research centre) of georgia ,u.s.a university to carry out a large amount of fundamental researchs in the disease and insect resistance research of plant and disease and pest interaction and oligosaccharides, and has obtained good laboratory and field effect in farm crop such as soybean, corn.Simultaneously, many in the world research institutions are also at the relevant oligose-type agricultural chemical product of active research exploitation.
Oligosaccharides since the sixties, it is found that the oligose fragment that the degrading plant cell walls obtains can induce the synthetic of plant protecting chemical as the fundamental research of plant immunization incitant.In isolated a series of active oligosaccharides, active best minimum meta oligosaccharides is poly-six sugar in β-Portugal as the formula (1) from the oligosaccharide mixture that obtains.Poly-six sugar in β-Portugal are one of the most activated oligosaccharides incitants of finding at present, and 1 gram oligosaccharides can make the tissue of 1000 tons of farm crop produce the plant protecting chemical of q.s.But what obtain with biodegradable method is a mixture, is difficult to purifying and measures considerably lessly, is difficult to practical requirement.Simultaneously, the polymerization degree size regulation and control that obtain of bio-degradation reactions have certain difficulty.Preparing poly-seven sugar (HSE) in β-Portugal so people begin to seek the method for chemosynthesis, is the very work of difficulty at the synthetic oligosaccharides of the eighties especially one seven sugar, along with the development of oligosaccharides synthetic technology makes this work become possibility.About the nineties, Ossowski, Fugedi, Lorentzen, groups such as Verduyn adopt different synthetic routes to finish the preparation of seven sugar in succession.These synthetic method routes are general much longer, and productive rate is unsatisfactory, and the reagent that uses is more expensive, and cost is very high, and is not suitable for suitability for industrialized production.1997, U.S. Nicolaou group synthesized poly-seven sugar (HSE) in Portugal with the method for solid phase synthesis, and this is a compelling job, but it is also unrealistic it to be developed into suitability for industrialized production.
The purpose of this invention is to provide the method for poly-six sugar in a kind of synthetic effectively β-Portugal, this building-up reactions route is short, and is easy and simple to handle, the yield height, and raw materials cost is low, has very high IP prospecting.
The invention provides the method for poly-six sugar in a kind of synthetic high reactivity oligose-type agricultural chemical β-Portugal, it is characterized in that: this method adopts Schmidt glucosides method under TMSOTf promotes, give body Segment A and trisaccharide receptor fragments B with the glucose trisaccharide, effectively dock, obtain six sugar, slough protecting group and promptly obtain poly-six sugar in β-Portugal with protecting group; In the structure of described Segment A, 2 hydroxyls of glucose are the Bz protecting group, and anomeric carbon is that body is given in the conduct of tribromo-acetyl imines ester,
The protecting group structure of Segment A and fragment B is as shown in the formula expression:
Wherein, Ac=CH
3(C=O)-, Bz=C
6H
5(C=O)-, Me=CH
3-.
In Segment A described in the present invention and fragment B synthetic; all obtain from intermediate disaccharides fragment C is synthetic; when fragment C and monose react to body; need not protect 4 hydroxyls of glucose; but utilize the different activities of 4,6 hydroxyls, carry out the selectivity glucosidesization; synthetic three required bglii fragments, the structure of fragment C are as shown in the formula expression:
The present invention has synthesized the glucose trisaccharide respectively and has given body and glucose three saccharide acceptors from glucose, adopts poly-six sugar in the Schmidt glucosides method Portugal that high productivity is protected under TMSOTf promotes, sloughs protecting group and promptly obtains poly-six sugar in β-Portugal.Trisaccharide segmental synthetic in, adopt the method for regioselectivity glucosidesization, thereby simplified reactions steps, make reaction scheme short, easy and simple to handle, the yield height, raw materials cost is low, has very high IP prospecting.
Particularly, the synthetic method of poly-six sugar in β-Portugal of the present invention can be carried out according to the following steps, and the present invention is not limited thereto certainly:
1) monose intermediate 3 is synthetic
With α-Pu Taotang first glycosides is raw material, and with 2, the reaction of 2-dimethylbenzaldehyde gets up to obtain intermediate 2 with 4,6 hydroxyl protections of glucose in the dry DMF solvent; Compound 2 is dissolved in the methylene dichloride, under triethylamine catalysis, with 1-benzoyl-benzotriazole (BzOBt) reaction, the hydroxyl that protection glucose is 2, has obtained 3 monose intermediates 3 that hydroxyl is exposed.
Its reaction process is shown in reaction formula (1):
2) monose is given the synthetic of body 5
With glucose is raw material, and reflux in sodium-acetate and acetic anhydride solution obtains full acetylated glucose, sloughs the ethanoyl of beginning carbon then with benzylamine, obtains compound 4; Compound 4 and Trichloroacetonitrile reaction obtain glucose tribromo-acetyl imines ester and give body 5.
Its reaction process is shown in reaction formula (2):
3) monose is given the synthetic of body 7
With glucose is raw material, with 6 hydroxyls of trityl group chlorine selective protection glucose, with acetic anhydride other hydroxyl protection is got up in the anhydrous pyridine solvent again, sloughs the ethanoyl of anomeric carbon then with benzylamine, obtains compound 6; Compound 6 and Trichloroacetonitrile reaction obtain glucose tribromo-acetyl imines ester and give body 7.
Its reaction process is shown in reaction formula (3):
4) disaccharides intermediate 9 (C) is synthetic
Monose acceptor 3 and glucose obtain disaccharides 8 for body 5 high yield under the promotion of trifluoromethanesulfonic acid trimethyl silicane (TMSOTf), and the mol ratio of TMSOTf and raw material is 0.8～1.2: 2; Compound 8 has obtained crucial disaccharides intermediate 9 (C) under 80% acetic acid effect.Its reaction process is shown in reaction formula (4):
5) trisaccharide intermediate 11 is synthetic
Disaccharides receptor 9 (C) and glucose give body 5 under the promotion of trifluoromethanesulfonic acid trimethyl silicane (TMSOTf), utilize the different activities of 4,6 hydroxyls, carry out the selectivity glycosylation reaction, obtain trisaccharide 10, and the mol ratio of TMSOTf and raw material is 0.8～1.2: 2; Compound 10 usefulness acetic anhydride/pyridine is converted into ethanoyl with anomeric carbon first glycosides after handling again in acetic anhydride/sodium-acetate/sulfuric acid mixed solution, obtain trisaccharide 12.
Its reaction process is shown in reaction formula (5):
6) trisaccharide is given the synthetic of body 14 (A)
Trisaccharide 12 is at N, and with the effect of acetic acid hydrazine, the ethanoyl of sloughing anomeric carbon obtains compound 13 in the dinethylformamide solvent; Compound 13 and Trichloroacetonitrile reaction obtain trisaccharide tribromo-acetyl imines ester and give body 14 (A).
Its reaction process is shown in reaction formula (6):
7) three saccharide acceptors is synthetic
Disaccharides receptor 9 (C) and glucose give body 7 under the promotion of trifluoromethanesulfonic acid trimethyl silicane (TMSOTf), carry out the selectivity glycosylation reaction, obtain trisaccharide 15, and the mol ratio of TMSOTf and raw material is 0.8～1.2: 2; After compound 15 usefulness acetic anhydride/pyridine is handled, handle with 80% acetum again and obtain three saccharide acceptors 17 (B).
Its reaction process is shown in reaction formula (7):
8) six sugar is synthetic
Three saccharide acceptors 17 (B) and glucose trisaccharide carry out the selectivity glycosylation reaction for body 14 (A) under the promotion of trifluoromethanesulfonic acid trimethyl silicane (TMSOTf), obtain six sugar 18 of full guard with good productive rate, the mol ratio of TMSOTf and raw material is 0.8～1.2: 2; After compound 18 usefulness sodium methylates are handled and sloughed protecting group, poly-six sugar 1 (I) in target molecule Portugal have promptly been obtained.
Its reaction process is shown in reaction formula (8):
Reaction product has been carried out with the NMR spectrometer of 400MHz
1H and
13C NMR characterizes.New compound has also carried out tests such as ultimate analysis, ESI mass spectrum, optically-active.
Below by embodiment technology of the present invention is given to illustrate further:
Synthesizing of embodiment 1 monose intermediate 3
(10.696g 55.08mmol) is dissolved in the 60ml dry DMF α-Pu Taotang first glycosides, adds tosic acid and regulates PH about 4, add 2 then, and the 2-dimethylbenzaldehyde (12.6g, 83.62mmol), bathing warm 50 ℃ of reactions 2 hours of reducing pressure down, TLC detects and shows that reaction is complete substantially.Et
3The N neutralization reaction, after the ethyl acetate dilution, water, saturated common salt water washing successively, dried over mgso.Concentrate the back airing.Obtain white solid 2 (14.93g), productive rate 96%;
Compound 2 (11.713g; 41.49mmol) be dissolved in the 80ml methylene dichloride; add 1-benzoyl-benzotriazole (9.926g; 41.49mmol); add the 6.42ml triethylamine then, room temperature reaction concentrated after 5 hours; column chromatography (sherwood oil: ethyl acetate 2: 1) obtain white solid 3 (13.79g), productive rate 86%.
1H?NMR(400MHz，CDCl
3， δppm)：8.10-7.37(m，10H，2×Bz)，5.55(s，1H，PhCH-)，5.07(d，1H，J＝4.0Hz，H-1)，5.03(dd，1H，J＝4.04,9.84Hz，H-2)，4.33(m，2H，H-5，H-6a)，3.88(m，1H，H-6b)，3.78(t，1H，H-4)，3.61(t，1H，H-3)，3.38(s，3H，CH
3)。
Embodiment 2 glucose are given the synthetic of body 5
(12.645g 32.39mmol) is dissolved in the 50ml anhydrous ether solution, and (4.31ml, 38.83mmol), reaction is spent the night under the room temperature to the system benzylamine under the ice bath with full acetylated glucose.Concentrate the back ethyl acetate extraction, use 1N hydrochloric acid soln, saturated NaHCO successively
3Solution, saturated common salt water washing.Concentrate back column chromatography for separation (sherwood oil: ethyl acetate 2: 1) obtain white solid 4 (9.24g), productive rate 90%.
(1.498g 4.30mmol) is dissolved in the 20ml anhydrous methylene chloride compound 4, adds 2.2mlCCl
3CN also drips DBU number droplet, stirs 2 hours under the room temperature.Concentrating under reduced pressure, the residue rapid column chromatography separates (sherwood oil: ethyl acetate 4: 1) obtain colourless syrup 5 (2.11g, 99.6%).
1HNMR(400?MHz，CDCl
3， δppm)：8.69(s，1H，NH)，6.55(d，1H，J＝3.8Hz，H-1)，5.55(t，1H，J＝9.7Hz，H-3)，5.17(t，1H，J＝9.6Hz，H-4)，5.12(dd，1H，J＝3.7Hz，H-2)，4.26(dd，1H，J＝4.0，12.1Hz，H-6)，4.20(m，1H，H-5)，4.12(dd，1H，J＝2.0，12.2Hz，H-6)，2.07(s，3H，OAc)，2.04(s，3H，OAc)，2.02(s，3H，OAc)and?2.01(s，3H，OAc)。
Embodiment 3 glucose are given the synthetic of body 7
Dextrose anhydrous (10.10g 56.06mmol), dissolves in the 80ml anhydrous pyridine, and adding TrCl (15.9g, 57.04mmol), 40 ℃ were reacted 6 hours down; In system, add 20mlAc subsequently
2The O room temperature reaction spends the night.In the reaction solution impouring frozen water, separate out white solid, filter, solid with acetic acid ethyl dissolution after, use 1N hydrochloric acid soln, saturated NaHCO successively
3Solution, saturated common salt water washing.Recrystallization in anhydrous methanol obtains full guard glucose 30.8g, productive rate 93%.
(17.15g 29.04mmol) is dissolved in the 100ml anhydrous ether solution, and (15ml, 5eq), reaction is spent the night under the room temperature to the system benzylamine under the ice bath with above-claimed cpd.Post-processing operation is with compound 4.Concentrate the back and obtain light yellow solid 6 (13.22g), productive rate 83% with sherwood oil and re-crystallizing in ethyl acetate.
1H?NMR(400MHz，CDCl
3， δppm)：7.44-7.20(m，15H，3×Bz)，5.52(d，1H，J＝3.52Hz，H-1)，5.48(t，1H，J＝9.90Hz，H-3)，5.20(t，1H，J＝9.92Hz，H-4)，4.97(dd，1H，J＝3.60，10.24Hz，H-2)，4.20(m，1H，H-5)，3.28-3.03(m，2H，H-6)，2.09(s，3H，OAc)，2.00(s，3H，OAc)and?1.73(s，3H，OAc)。
(0.576g 1.05mmol) is dissolved in the 5ml anhydrous methylene chloride compound 6, adds 0.5mlCCl
3CN also drips DBU number droplet, stirs 3 hours under the room temperature.Concentrating under reduced pressure, the residue rapid column chromatography separates (sherwood oil: ethyl acetate 5: 1) obtain colourless syrup 5 (0.623g, 85.6%).Be directly used in next step reaction.
Synthesizing of embodiment 4 disaccharides intermediates 8
Monose acceptor 3 (1.00g, 2.59mmol), glucose give body 5 (1.605g, 3.26mmol) and 4 molecular sieves be dissolved in the anhydrous CH of 30ml
2Cl
2In, under the argon shield, stirring at room 2 hours.Be chilled to-78 ℃, drip TMSOTf (0.05N, CH 2.5ml)
2Cl
2Solution reacted after 1 hour, dripped triethylamine quencher reaction.Filter, concentrate back column chromatography for separation (sherwood oil: ethyl acetate 3: 1) obtain disaccharides 8 (2.12g), productive rate 94%.
1H?NMR(400MHz，CDCl
3， δppm)：8.08-7.33(m，10H，2×Bz)，5.60(s，1H，PhCH-)，5.12(dd，III，J＝4.0，10.0Hz，H-2)，5.07-4.97(m，4H)，4.78(d，1H，J＝7.8Hz，H-1’)，4.38(t，1H，J＝9.86Hz)，4.30(dd，1H，J＝4.25，9.8Hz)，4.19(dd，1H，J＝4.40，12.23Hz)，4.02-3.88(m，2H)，3.83(t，1H，J＝10.04Hz)，3.74(t，1H，J＝9.20Hz)3.60(m，1H)，3.39(s，3H，CH
3)，1.98(s，3H，OAc)，1.97(s，3H，OAc)，1.90(s，3H，OAc)and?1.55(s，3H，OAc)。
Synthesizing of embodiment 5 disaccharides receptor 9s (C)
(l.95mmol) 1.433g is dissolved in the acetic acid of 20ml80% to disaccharides 8,60 ℃ of reacting by heating 2 hours.After reaction solution concentrated, saturated NaHCO was used in the ethyl acetate dilution successively
3Solution, water, saturated common salt water washing.Concentrate back column chromatography for separation (sherwood oil: ethyl acetate 1: 1) obtained crucial disaccharides intermediate 9 (C) (1.01g), productive rate 80.1%.[α]
D 2464.1 ° (c0.68, CHCl
3);
1H NMR (400MHz, CDCl
3, δ ppm): 8.08-7.48 (m, 5H, Bz), 5.13 (t, 1H, J=9.4Hz), 5.06-4.97 (m, 4H), 4.70 (d, 1H, J=8.0Hz, H-1 '), 4.22-4.21 (m, 2H), 4.07 (t, 1H, J=9.4Hz), 3.94 (dd, 1H, J=3.04,11.96Hz), 3.85-3.81 (m, 2H), 3.74-3.64 (m, 2H), 3.39 (s, 3H, CH
3), 2.11 (s, 3H, OAc), 2.03 (s, 3H, OAc), 1.93 (s, 3H, OAc) and 1.37 (s, 3H, OAc); ESI MS (m/z): 1886 (3M
+), 1258 (2M
++ 1), 651 (M
++ 1) (100%), 646 (M
++ H
2O), 331,169; Ultimate analysis C
28H
36O
161/2H
2O: manage the value C that sinks, 52.74; H, 5.85. measured value C, 52.92; H, 6.08.
Synthesizing of embodiment 6 trisaccharide intermediates 10
(1.99g 3.09mmol) is dissolved in the anhydrous CH of 6ml with 4 MS to disaccharides receptor 9 (C)
2Cl
2In, under the argon shield, stirring at room 30 minutes.Be chilled to-78 ℃, drip TMSOTf (0.05N, CH 3.0ml)
2Cl
2Solution drips monose subsequently and gives body 5 (1.75g, CH 3.55mol)
2Cl
2Solution reacted after 1 hour, triethylamine quencher reaction.Filter, concentrate back column chromatography for separation (sherwood oil: ethyl acetate 1: 1) obtain trisaccharide 10 (2.33g), productive rate 77%.[α]
D 2428.4 ° (c 1.11, CHCl
3);
1H NMR (400MHz, CDCl
3, δ/ppm): 8.06-7.48 (m, 5H, Ph-H), 5.22 (t, 1H, J=9.48Hz), 5.13-4.95 (m, 7H), 4.67 (d, 1H, J=8.04Hz, H-1), 4.63 (d, 1H, J=7.96Hz, H-1), 4.28-4.16 (m, 5H), 4.03 (t, 1H), and 3.83-3.72 (m, 4H), 3.51 (t, 1H, J=8.84Hz), 3.45 (s, 3H, CH
3), 2.11 (s, 3H, OAc), 2.10 (s, 3H, OAc), 2.09 (s, 3H, OAc), 2.04 (s, 3H, OAc), 2.03 (s, 6H, 2 * OAc), 2.01 (s, 3H, OAc), 1.93 (s, 3H, OAc) and 1.39 (s, 3H, OAc); ESI MS (m/z): 1940 (2M
++ Na), 982 (M
++ Na) (100%), 977 (M
++ H
2O), 976,331; Ultimate analysis C
42H
54O
251/2H
2O: calculated value C, 52.12; H, 5.73. measured value C, 52.04; H, 5.83.
Synthesizing of embodiment 7 trisaccharide intermediates 12
(3.77g 3.71mmol) is dissolved in reacting in the mixing solutions of 20ml pyridine and 4ml acetic anhydride and spends the night compound 10.After concentrating, residue is dissolved in 24mlAc
2O, adds 18mlAc by 0 ℃
2O/18mlAcOH/0.84mlH
2SO
4Mixing solutions, room temperature reaction is after 10 hours, through conventional aftertreatment, again through column chromatography for separation (sherwood oil: ethyl acetate 1: 1) obtain trisaccharide 12 (3.01g), productive rate 78%.[α]
D 2424.4 ° (c 0.71, CHCl
3);
1H NMR (400MHz, CDCl
3, δ/ppm): 7.99-7.49 (m, 5H, Ph-H), 6.38 (d, 1H, J=3.6Hz), 5.24-5.19 (m, 2H), 5.13-4.87 (m, 5H), 4.67 (d, 1H, J=7.6Hz), 4.53 (d, 1H, J=8.0Hz), 4.44-3.96 (m, 8H), and 3.77-3.65 (m, 2H), 3.50 (m, 1H), 2.63 (s, 3H, CH
3), 2.19 (s, 3H, OAc), 2.09 (s, 9H, 3 * OAc), 2.05 (s, 3H, OAc), 2.02 (s, 3H, OAc), 2.00 (s, 6H, 2 * OAc), 1.90 (s, 3H, OAc) and 1.65 (s, 3H, OAc); ESI MS (m/z): 1052 (M
++ Na) (100%), 1051,1047 (M
++ H
2O), 1046,970,331; Ultimate analysis C
45H
56O
271/2H
2O: calculated value C, 52.07; H, 5.54. measured value C, 52.02; H, 5.54.
Embodiment 8 trisaccharides are given the synthetic of body 14 (A)
Trisaccharide 12 (1.353g 1.29mmol) is dissolved in 15mlDMF, and adding acetic acid hydrazine (0.134g, 1.45mmol), stirring at room was reacted after 2 hours, in reaction solution impouring water, and ethyl acetate extraction, after dry the concentrating, obtain trisaccharide 13 (1.27g), productive rate 98% through column chromatography for separation; [α]
D 24-4.7 ° (c 0.72, CHCl
3);
1H NMR (400MHz, CDCl
3, δ/ppm): 8.07-7.29 (m, 5H, Ph-H), 5.49 (d, 1H, J=2.53Hz, H-1), 5.23-4.85 (m, 8H), 4.71 (d, 1H, J=7.96Hz, H-1), 4.57 (d, 1H, J=7.79Hz, H-1), 4.43-4.35 (m, 2H), 4.27-4.06 (m, 4H), 3.90 (m, 1H), 3.72-3.60 (m, 3H), 2.09 (s, 6H, 2 * OAc), 2.07 (s, 6H, 2 * OAc), 2.03 (s, 6H, 2 * OAc), 2.01 (s, 3H, OAc), 2.00 (s, 3H, OAc) and1.89 (s, 3H, OAc); ESI MS (m/z): 1019 (M
++ MeOH) (100%), 970 (M
+-OH), 331; Ultimate analysis C
43H
54O
26: calculated value C, 52.33; H, 5.52. measured value C, 52.26; H, 5.62.
(1.616g 1.61mmol) is dissolved in the 10ml anhydrous methylene chloride compound 13, adds 0.5ml CCl
3CN also drips DBU number droplet, stirs 3 hours under the room temperature.Concentrating under reduced pressure, (sherwood oil: ethyl acetate 1: 1) obtain trisaccharide and give body 14 (A) (1.516g), productive rate is 82% to the separation of residue rapid column chromatography.Be directly used in next step reaction.
1H?NMR(400MHz，CDCl
3，δ/ppm)：8.62(s，1H，NH)，8.00-7.27(m，5H，Ph-H)，6.57(bs，1H，H-1)，5.41-4.86(m，8H)，4.65(d，1H，J＝7.58Hz，H-1)，4.58(d，1H，J＝7.88Hz，H-1)，4.42-3.98(m，7H)，3.74-3.55(m，3H)，2.09(s，6H，2×OAc)，2.05(s，3H，OAc)，2.03(s，3H，OAc)，2.01(s，6H，2×OAc)，1.99(s，3H，OAc)，1.89(s，3H，OAc)and?1.67(s，3H，OAc)。
Synthesizing of embodiment 9 trisaccharide intermediates 15
(1.51g 2.34mmol) is dissolved in the anhydrous CH of 20ml with 4 MS (3g) to disaccharides receptor 9 (C)
2Cl
2In, under the argon shield, stirring at room 2 hours.Be chilled to-78 ℃, drip TMSOTf (0.05N, CH 2.2ml)
2Cl
2Solution drips monose subsequently and gives body 7 (1.78g, CH 2.56mmol)
2Cl
2Solution reacted after 2 hours, triethylamine (0.1ml) quencher reaction.Filter, (sherwood oil: ethyl acetate 1.5: 1) obtain trisaccharide 15 (2.21g), productive rate is 80.4% to concentrate the back column chromatography for separation.[α]
D 2450.0 ° (c 1.19, CHCl
3);
1H NMR (400MHz, CDCl
3, δ/ppm): 8.08-7.20 (m, 20H, 4 * Bz), 5.20-4.96 (m, 8H), 4.68 (d, 1H, J=8.00Hz, H-1), 4.65 (d, 1H, J=7.60Hz, H-1), 4.37-4.07 (m, 4H), 3.89-3.74 (m, 3H), 3.59-3.53 (m, 2H), 3.37 (s, 3H, CH
3), 3.29 (dd, 1H, J=2.2,10.64Hz), 3.09 (dd, 1H, J=4.6,10.56Hz), 2.05 (s, 3H, OAc), 2.03 (s, 3H, OAc), 2.02 (s, 3H, OAc), 1.99 (s, 3H, OAc), 1.93 (s, 3H, OAc), 1.73 (s, 3H, OAc) and 1.40 (s, 3H, OAc) .ESI MS (m/z): 1218 (M
++ Na+2H
2O) (100%), 1177 (M
++ H
2O), 694,970,331,243; Ultimate analysis C
59H
66O
24: juice calculation value C, 61.13; H, 5.74. measured value C, 61.23; H, 5.88.
Synthesizing of embodiment 10 3 saccharide acceptors 17 (B)
(1.20g 1.02mmol) is dissolved in reacting in the mixing solutions of 10ml pyridine and 3ml acetic anhydride and spends the night compound 15.After concentrating, residue is dissolved in the anhydrous CH of 20ml
2Cl
2In, add FeCl
3H
2O (533mg), stirring at room 5 hours.After the washing, dry concentrating.(sherwood oil: ethyl acetate 1: 1) obtain trisaccharide 17 (B) (0.907g), productive rate is 96% to column chromatography for separation.[α]
D 2430.3 ° (c 0.85, CHCl
3);
1H NMR (400MHz, CDCl
3, δ/ppm): 8.06-7.50 (m, 5H, Ph-H), 5.26 (t, 1H, J=9.6Hz), 5.06-4.86 (m, 8H), 4.69 (d, J=7.92Hz, H-1), 4.59 (d, 1H, J=8.0Hz, H-1), 4.39 (dd, 1H, J=4.4,12.4Hz), 4.27 (t, 1H, J=9.52Hz), 4.09-3.91 (m, 3H), 3.77-3.53 (m, 5H), 2.63 (s, 3H, CH
3), 2.09 (s, 3H, OAc), 2.07 (s, 3H, OAc), 2.06 (s, 6H, 2 * OAc), 2.02 (s, 3H, OAc), 1.99 (s, 3H, OAc), 1.89 (s, 3H, OAc) and 1.59 (s, 3H, OAc); ESI MS (m/z): 1941 (2M
++ Na), 1936 (2M
++ H
2O), 981 (M
++ Na-1), 976 (M
++ H
2O-1) (100%), 332; Ultimate analysis C
42H
54O
25H
2O: calculated value C, 51.64; H, 5.78. measured value C, 51.85; H, 5.74.
Synthesizing of embodiment 11 6 sugar precursors 18
Three saccharide acceptors 17 (B) (0.323g, 0.337mmol), trisaccharide give body 14 (A) (0.456g, 0.403mmol) and 4 molecular sieves (lg) be dissolved in the anhydrous CH of 20ml
2Cl
2In, under the argon shield, stirring at room 2 hours.Be chilled to-78 ℃, drip TMSOTf (0.05N, CH 0.66ml)
2Cl
2Solution reacted after 1 hour, dripped triethylamine quencher reaction.Filter, concentrate back column chromatography for separation (sherwood oil: ethyl acetate 1: 1 → 1: 2) obtain six sugar 18 (0.548g), productive rate 84.4%.[α]
D 248.2 ° (c 0.87, CHCl
3);
1H NMR (400MHz, CDCl
3, δ/ppm): 8.10-7.51 (m, 10H, 2 * Bz), 5.24-5.14 (m, 2H), 5.10-4.93 (m, 5H), 4.92-4.76 (m, 7H), 4.75 (d, 1H, J=7.9Hz, H-1), 4.62 (m, 1H), 4.58 (d, 1H, J=8.0Hz, H-1), 4.54 (m, 1H), 4.42-4.38 (m, 2H), and 4.30-3.27 (m, 3H), 4.1 5-4.03 (m, 5H), 3.96-3.47 (m, 10H), 3.34 (s, 3H, CH
3), 3.22 (m, 1H), 2.12 (s, 3H, OAc), 2.11 (s, 6H, 2 * OAc), 2.08 (s, 3H, OAc), 2.07 (s, 3H, OAc), 2.06 (s, 3H, OAc), 2.05 (s, 3H, OAc), 2.04 (s, 3H, OAc), 2.02 (s, 3H, OAc), 2.00 (s, 6H, 2 * OAc), 1.98 (s, 3H, OAc), 1.97 (s, 3H, OAc), 1.93 (s, 3H, OAc), 1.89 (s, 6H, 2 * OAc) and 1.85 (s, 3H, OAc); ESI MS (m/z): 1968 (M
++ K+1), 1949 (M
++ Na-1), 1947 (M
++ H
2O+1) (100%), 1929 (M
++ 1), 1927,984; Ultimate analysis C
85H
106O
50H
2O: calculated value C, 52.46; H, 5.65. measured value C, 52.38; H, 5.76.
Synthesizing of embodiment 12 6 sugar 1
(0.128g 0.067mmol) is suspended in the anhydrous methanol compound 18, and (1M 1.4ml), stirs under the room temperature and spends the night the methanol solution of dropping sodium methylate.The TLC detection reaction is complete substantially, resin cation (R.C.) (H
+Type) neutralization is filtered, and concentrates, and column chromatography for separation has obtained target molecule six sugar 1 (65mg), productive rate 97%.
1H?NMR(400MHz，D
2O，δ/ppm)：4.80(d，1H，H-1)，4.72(d，1H，J＝Hz，H-1)，4.68(d，1H，J＝7.92Hz，H-1)，4.52(d，1H，J＝7.92Hz，H-1)，4.49(d，1H，J＝7.92Hz，H-1)，4.49(d，1H，J＝7.92Hz，H-1)，4.62(d，1H，H-1)，4.58(d，1H，J＝7.92Hz，H-1)，4.22-4.15(m，2H)，3.91-3.3.76(m，8H)，3.75-3.65(m，6H)，3.62-3.58(m，4H)，3.52-3.29(m，16H)，3.42(s，3H，CH
3)；
13C?NMR(100MHz，D
2O，δ/ppm)：105.5，105.4，105.4，105.4，105.3，101.8，86.7，84.7，78.5，78.5，78.1，78.1，78.1，77.4，77.2，76.0，76.0，75.6，75.6，75.4，73.3.73.0，72.1，72.1，72.1，72.0，72.0，71.4，71.1，71.1，70.5，70.3，70.3，63.2，63.2，63.2，57.8。
Claims (2)
1. the method for poly-six sugar in a synthetic high reactivity oligose-type agricultural chemical β-Portugal, it is characterized in that: this method adopts Schmidt glucosides method under TMSOTf promotes, give body Segment A and trisaccharide receptor fragments B with the glucose trisaccharide, effectively dock, obtain six sugar, slough protecting group and promptly obtain poly-six sugar in β-Portugal with protecting group; In the structure of described Segment A, 2 hydroxyls of glucose are the Bz protecting group, and anomeric carbon is that body is given in the conduct of tribromo-acetyl imines ester,
The protecting group structure of Segment A and fragment B is as shown in the formula expression:
Wherein, Ac=CH
3(C=O)-, Bz=C
6H
5(C=O)-, Me=CH
3-.
2. the method for gathering six sugar according to the described synthetic high reactivity oligose-type agricultural chemical of claim 1 β-Portugal, it is characterized in that: described Segment A and fragment B's is synthetic, all obtain from intermediate disaccharides fragment C is synthetic, when fragment C and monose react to body, utilize the different activities of 4,6 hydroxyls, carry out the selectivity glucosidesization, synthetic three required bglii fragments, the structure of fragment C are as shown in the formula expression:
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| CNB001229435A CN1172957C (en) | 2000-08-30 | 2000-08-30 | Process for preparing beta-6-dextran as high-activity oligose-type agricultural chemical |
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|---|---|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212087A (en) * | 2011-01-24 | 2011-10-12 | 南京工业大学 | Method for preparing 3, 6-branched glucose trisaccharide |
| CN108912239A (en) * | 2018-06-19 | 2018-11-30 | 朱玉亮 | A kind of synthetic method of poly- seven sugar in 3,6 branching Portugals |
-
2000
- 2000-08-30 CN CNB001229435A patent/CN1172957C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102212087A (en) * | 2011-01-24 | 2011-10-12 | 南京工业大学 | Method for preparing 3, 6-branched glucose trisaccharide |
| CN108912239A (en) * | 2018-06-19 | 2018-11-30 | 朱玉亮 | A kind of synthetic method of poly- seven sugar in 3,6 branching Portugals |
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