CN1379036A - Phenylethanol boschnaloside compounds - Google Patents

Phenylethanol boschnaloside compounds Download PDF

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CN1379036A
CN1379036A CN 02117641 CN02117641A CN1379036A CN 1379036 A CN1379036 A CN 1379036A CN 02117641 CN02117641 CN 02117641 CN 02117641 A CN02117641 A CN 02117641A CN 1379036 A CN1379036 A CN 1379036A
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compound
compounds
meoh
glc
glycosides
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CN1156487C (en
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屠鹏飞
雷丽
宋志宏
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COLLEGE OF PHARMACY BEIJING UNIV
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Abstract

A group of 7 novel phenylethanol glycoside compounds is extracted from cistanche by chromatography with silica gel column, macroporous adsorption resin and glucosan gel LH-20 column and efficient liquid-phase chromatography. It has the function of resisting nerve cell withering.

Description

One group of Chinese medicine Herba Cistanches benzyl carbinol glycosides compounds
Technical field: the present invention relates to separating effective ingredient from Cistanche Hoffmgg. et Link plants, particularly relate to the new benzyl carbinol glycosides compounds of separation from three kinds of Cistanche Hoffmgg. et Link plants.
Background technology: Cistanche Tubulosa [Cistanche.tubulosa (Schenk) R.Wight], Herba Cistanches sinensis (C.sinensisG.Beck) and Saline Cistanche Herb C.salsa (C.A.Mey.) G.Beck are that Orobanchaceae Orobanchaceae Herba Cistanches belongs to the perennial parasitic herbaceous plant of Cistanche.Chinese medicine Herba Cistanches Herba Cistanches is the chylocaulous of this platymiscium arid zones scale leaf, beginning is stated from Shennong's Herbal, classify as top grade, the effect that have kidney-replenishing, benefiting essence-blood, relaxes bowel, cure mainly diseases such as impotence in male, infertilitas feminis, blood depletion constipation, the good reputation of " desert genseng " is arranged.The frequency that occurs in the kidney-replenishing prescription is the highest.
Chemical constitution study to Herba Cistanches starts from early eighties, and Japanese scholar has made extensive work to this.At that time, Japan for solve the aging problem and take up to excavate and exploitation to geriatric disease, the effective medicine of senile dementia particularly is used as kidney tonifying, establishing-Yang, strong smart medicine for a long time based on Herba Cistanches and is used for clinically, becomes the object of being furtherd investigate.The late nineteen eighties, Chinese scholar begins to pay close attention to the chemical ingredients of homemade Herba Cistanches.Cistanche Hoffmgg. et Link plants mainly contains compositions such as benzyl carbinol glycosides, iridoid and glycoside thereof, lignanoid and glycosides thereof.Wherein, the benzyl carbinol glycosides compounds is the main component of Cistanche Hoffmgg. et Link plants, also is main activeconstituents (Sato, T.Kozima, et al.Yakugaku Zasshi, 105 (12): 1131,1985; He Wei etc. CHINA JOURNAL OF CHINESE MATERIA MEDICA, 21 (9): 564,1996).Be divided at present from obtaining 22 compounds, comprise 1 monoglycosides, 14 disaccharide glycosides and 7 three glucosides.Many pieces of bibliographical informations the benzyl carbinol glycosides compounds have many-sided biologic activity, have certain DEVELOPMENT PROSPECT (Jimenez C, et al.NatProd Rep, 11 (6): 591,1994; Cometa S, et al.Fitoterapia, 64 (3): 195,1993).7 compounds of the present invention have had not yet to see report.
Summary of the invention: the present invention seeks to the chemical ingredients of systematic study Cistanche Hoffmgg. et Link plants Cistanche Tubulosa, Saline Cistanche Herb and Herba Cistanches sinensis, seek the reactive monomer compound.
Invention is achieved in that
Utilize multiple separation means, comprise silica gel column chromatography, macroporous adsorbent resin, sephadex lh-20 column chromatography and preparative high performance liquid chromatography etc., the chemical ingredients of the above-mentioned three kinds of Herba Cistanchess of systematic study.Be separated to 32 monomer components from Cistanche Tubulosa, wherein 3 is new benzyl carbinol glycosides compounds, is respectively pipe flower glycosides A (Cistantubuloside A), pipe flower glycosides B 1/ B 2(Cistantubulosides B 1/ B 2), pipe flower glycosides C 1/ C 2(Cistantubulosides C 1/ C 2); From Saline Cistanche Herb, be separated to 20 compounds, wherein 3 is new benzyl carbinol glycosides compounds, be respectively Isotubuloside E (Isotubuloside E), 2 '-2'-acetylosmanthuside (2 '-Acetylosmanthuside), 2 '-2'-acetylcistanoside C (2 '-AcetylcistanosideC); Be separated to 12 compositions in the Herba Cistanches sinensis, 1 new benzyl carbinol glycosides compounds is arranged, be Cistansinenside A (Cistansinenside A).
Embodiment 1
Compound 1,2 and 3
1, extraction separation
95% alcohol reflux of Cistanche Tubulosa dry meat stem 36.0kg is evaporated to the medicinal extract shape, with an amount of H 2The O suspendible is used sherwood oil, ethyl acetate and n-butanol extraction successively, reclaims solvent and gets n-butyl alcohol extract 4.0kg.Get n-butyl alcohol extract 500g and carry out D 101Macroporous adsorbent resin column chromatography is with H 2O, 10%EtOH, 30%EtOH, 50%EtOH, 70%EtOH be wash-out successively, obtains H behind the concentrating under reduced pressure respectively 2O part (290.0g), 30%EtOH part (76.0g).
30%EtOH part (15.0g) gets 16 streams part (Fr.I-XVI) through reversed-phase silica gel column chromatography (RP-18,100-120 order) 25% → 75%MeOH gradient elution.Fr.IV (1.0g) is through Sephadex LH-20 column chromatography, and the 50%MeOH wash-out gets 10 streams part (Fr.1～10).Fr.5 (0.22g) through 2 HPLC, half preparation separate compound 1 (23mg) (structural formula 1), 2 (6a, 6b) (22mg) (structural formula 2).
H 2O part (140.0g) is through Diaion HP20 macroporous adsorbent resin column chromatography, H 2O → MeOH gradient elution gets 7 streams part (Fr.I-VII).Fr.V (3.0g) is through Sephadex LH-20 column chromatography, H 2O → 30%MeOH gradient elution gets 9 stream parts.Wherein the 6th and 7 streams part (1.0g) are through reversed-phase silica gel column chromatography (RP-18,100-120 order), and 20% → 70%MeOH gradient elution gets 7 streams part (Fr.1-7).Fr.5 (0.2g) gets compound 3 (11mg) (structural formula 3) through partly preparing HPLC purifying repeatedly.
2, structure is identified
Mainly utilize spectrum, comprise ultraviolet, infrared, mass spectrum, nuclear magnetic resonance spectrum ( 1HNMR, 13CNMR, 2D-NMR) and FAB-MS, HRSI-MS analysis (table 1,2,3,4), its structure identified.
Utilization 2D-NMR technology, especially COSY, HMQC and HMBC spectrum have solved the link position of substituent position and sugar, in conjunction with high resolution mass spectrum, their whole hydrogen signals have been carried out definite ownership.
Embodiment 2
Compound 4
1, extraction separation
Herba Cistanches sinensis crude drug 3.1Kg uses 95% alcohol reflux, behind the extracting solution concentrating under reduced pressure with an amount of H 2The O suspendible is used sherwood oil, ethyl acetate and n-butanol extraction successively, reclaims solvent.Acetic acid ethyl ester extract 160g is carried out silica gel column chromatography (200～300 order), CHCl 3-MeOH (9: 1 → 2: 1) gradient elution gets 8 streams part (Fr.I-VIII), and Fr.V (12.0g) carries out polyamide column chromatography (TLC polymeric amide), and 30%～70%MeOH gradient elution gets Fr.1～7.Fr.3 (0.25g) is through Sephadex LH-20 column chromatography, and the 50%MeOH wash-out gets the crude product (12mg) of compound 4, gets compound 4 (6.0mg) (structural formula 4) through the HPLC purifying again.
2, structure is identified
Mainly utilize spectrum, comprise ultraviolet, infrared, mass spectrum, nuclear magnetic resonance spectrum ( 1HNMR, 13CNMR, 2D-NMR) and FAB-MS, HRSI-MS analysis (table 5), its structure identified.
Utilization 2D-NMR technology, especially COSY, HMQC and HMBC spectrum have solved the link position of substituent position and sugar, in conjunction with high resolution mass spectrum, their whole hydrogen signals have been carried out definite ownership.
Embodiment 3
Compound 5,6 and 7
1, extraction separation
The 75% ethanol percolation liquid of Saline Cistanche Herb dry meat stem 8Kg is evaporated to the medicinal extract shape, with an amount of H 2The O suspendible is successively with sherwood oil, ethyl acetate and n-butanol extraction.Acetic acid ethyl ester extract 99g is separated through silica gel (200-300 order) column chromatography, get 9 cuts with chloroform to the solution gradient wash-out of chloroform-methanol (1: 2) different ratios successively, cut 5 separates through Sephadex LH-20 chromatographic column, and the methanol-water with 50% is an eluent, obtains 11 parts.Wherein, 6-7 (2.5g) utilizes reversed-phase silica gel column chromatography (RP-18 again, the 100-200 order), get 35 cut Fr. (1-35) with 10%-50% methyl alcohol gradient elution, merge Fr.26-32 (350mg), separate with Sephaex LH-20 column chromatography, 20% methyl alcohol is made eluent, obtain 20 cuts, cut 8 (45mg) separates (C through partly preparing HPLC 18Post, CH 3CN-MeOH-H 2O 10: 20: 70,2.2ml/min, 330nm and 254nm dual wavelength detect), get compound 5 (22mg) (structural formula 5); Cut 10 (36mg) separates (C through partly preparing HPLC 18Post, CH 3CN-MeOH-H 2O 9: 18: 73,2.5ml/min, 330nm and 254nm dual wavelength detect), get compound 6 (20mg) (structural formula 6); Cut 16 and 17 merges (40mg) and separates (C through partly preparing HPLC 18Post, CH 3CN-MeOH-H 2O 10: 16: 74,2.2ml/min, 330nm and 254nm dual wavelength detect), get compound 7 (18mg) (structural formula 7).
2, structure is identified
Mainly utilize spectrum, comprise ultraviolet, infrared, mass spectrum, nuclear magnetic resonance spectrum ( 1HNMR, 13CNMR, 2D-NMR) and FAB-MS, HRSI-MS, HRESI-MS analyze (table 6,7,8), identify its structure.
Utilization 2D-NMR technology, especially HMQC and HMBC spectrum has solved the link position of substituent position and sugar, in conjunction with high resolution mass spectrum, their whole hydrogen signals has been carried out definite ownership.
The structure of new benzyl carbinol glycosides compounds 1-7
Compound 1 pipe flower glycosides A (Cistantubuloside A)
Figure A0211764100081
Compound 2 pipe flower glycosides B 1/ B 2(Cistantubulosides B 1/ B 2)
Figure A0211764100082
Compound 3 pipe flower glycosides C 1/ C 2Cistantubulosides C 1/ C 2
Figure A0211764100091
Compound 4 Cistansinenside As (Cistansinenside A)
Compound 52 '-2'-acetylcistanoside C (2 '-Acetylcistanoside C)
Compound 62 '-2'-acetylosmanthuside (2 '-Acetylosmanthside)
Compound 7 Isotubuloside Es (Isotubuloside E)
Figure A0211764100102
The physicochemical constant of table 1. compound 1-7 and main spectroscopic data compound 1
Molecular formula is C 35H 46O 19, be faint yellow amorphous powder, UV 365Following apparent blue-fluorescence, FeCl 3-K 3[Fe (CN) 6] show blue.FABMS(posit.)m/z：809(M+K) +，793(M+Na) +，771(M+H) +，609(M+H-Glc) +，471(M+H-Glc-Aglycone) +，463(M+H-Glc-Rha) +，325(M+H-Glc-Rha-Aglycone) +，163(Caffeoyl) +，121(Aglyone+H-OH) +。HRSIMS(neg.)m/z：769.2559(M-H) -。 1HNMR (400MHz, DMSO-d 6): see Table 2. 13CNMR (100MHz, DMSO-d 6): see Table 3.Compound 2
Molecular formula is C 35H 46O 19, pale yellow powder, UV 365Following apparent blue-fluorescence, FeCl 3-K 3[Fe (CN) 6] show blue.FABMS(posit.)m/z：809(M+K) +，793(M+Na) +，771(M+H) +，609(M+H-Glc) +，463(M+H-Glc-Rha) +，455(M+H-Glc-Aglycone) +，309(M+H-Glc-Rha-Aglycone) +，147(Coumaroyl) +。HRSIMS(neg.)m/z：769.2562(M-H) -。 1HNMR (400MHz, DMSO-d 6): see Table 2. 13CNMR (100MHz, DMSO-d 6): see Table 3.Compound 3
Molecular formula is C 35H 46O 21, pale yellow powder, UV 365Following apparent blue-fluorescence, FeCl 3-K 3[Fe (CN) 6] show blue.FABMS(posit.)m/z：841(M+K) +，825(M+Na) +，803(M+H) +，785(M+H-H 2O) +。HRSIMS(neg.)m/z：801.2478(M-H) -。 1HNMR (600MHz, MeOH-d 4), 13CNMR (150MHz, MeOH-d 4): see Table 4.Compound 4
Molecular formula is C 32H 40O 16Pale yellow powder, UV 365Following apparent blue-fluorescence, FeCl 3-K 3[Fe (CN) 6] show blue.FABMS(posit.)m/z：719(M+K) +，703(M+Na) +，681(M+H) +，534(M+H-Rha) +，513(M+H-Aglycone) +，367(M+H-Rha-Aglycone) +，163(Caffeoyl) +，151(Agly-cone+H?OH) +。HRSIMS(neg.)m/z：679.2227(M-H) -。 1HNMR (500MHz, MeOH-d 4), 13CNMR (125MHz, MeOH-d 4): see Table 5.Compound 5
Molecular formula is C 32H 39O 16Light yellow amorphous powder, 5%FeCl 3Show pewter, UV 365Following apparent sapphirine fluorescence.FAB-MS(neg.)m/z：679(M-H) -，553(M-H-Rha) -；HRSI-MS(neg.)(m/z)：679.2228(M-H) -。 1HNMR (500MHz, MeOH-d 4), 13CNMR (125MHz, MeOH-d 4): see Table 6.Compound 6
Molecular formula is C 31H 38O 15Light yellow amorphous powder, 5%FeCl 3Show pewter, UV 365Following apparent sapphirine fluorescence FAB-MS (neg.) m/z:649 (M-H) -, 443 (M-H-AC-Caffeoyl) -HRESI-MS (m/z): 668.2563 (M+NH 4) + 1HNMR (500MHz, DMSO-d 6), 13CNMR (125MHz, DMSO-d 6): see Table 7.Compound 7
Molecular formula is C 31H 38O 15Light yellow amorphous powder, 5%FeCl 3Colour developing is pewter, UV 365Following apparent sapphirine fluorescence.FAB-MS(neg.)m/z：649(M-H) -；HRESI-MS(m/z)：668.2543(M+NH 4) +。 1HNMR (500MHz, DMSO-d 6), 13CNMR (125MHz, DMSO-d 6): see Table 8.Table 2. compound 1,2 1(δ, solvent are DMSO-d to the HNMR chemical displacement value 6) sequence number compound 1 compound 2
Aglycone
2 7.06(d，84) 6.64(s)
3 6.67(d，8.4) --
5 6.67(d，8.4) 6.63(d，8.0)
6 7.06(d，8.4) 6.51(dd，8.0，1.5) α(8) 3.64 3.63
3.91(dd，9.7，7.6) 3.89(m) β(7) 2.76(br.t，7.4) 2.70(m)
Ester
2 7.03(br.s) 7.53(d，8.5) 7.69(d，8.6)
3 -- 6.80(d，8.5) 6.76(d，8.6)
5 6.76(d，8.1) 6.80(d，8.5) 6.76(d，8.6)
6 6.99(dd，8.1，1.3) 7.53(d，8.5) 7.69(d，8.6) α(8) 6.21(d，15.9) 6.35(d，15.9) 5.71(d，12.8) β(7) 7.47(d，15.9) 7.56(d，15.9) 6.94(d，12.8)
Glc
1 4.37(d，7.8) 4.37(d，7.8) 4.36(d，7.8)
2 3.21(t，8.4) 3.22 3.26
3 3.72 3.72 3.68
4 4.70(t，9.7) 4.72(t，9.7) 4.63(t，9.7)
5 3.73 3.74 3.72
6 3.50(dd，11.8，7.1) 3.50(dd，11.7，6.7)
3.66 3.67
Rha
1 5.03(br.s) 5.03(s)
2 3.69 3.68
3 3.28 3.30
4 3.11 3.10
5 3.38 3.35 3.40
6 0.96(d，6.1) 0.95(d，6.1) 1.04(d，6.1)
Glc′
1 4.18(d，7.7) 4.16(d，7.6) 4.17(d，7.6)
2 2.94(t，8.2) 2.94(t，8.2)
3 3.10 3.08
4 3.02 3.04
5 3.00 3.03
6 3.39 3.40
3.62 3.64 table 3. compounds 1,2 13(δ, solvent are DMSO-d to the CNMR chemical displacement value 6) carbon atom compound 1 compound 2 carbon atom compounds 1 compound 2Aglycone Glc 1 128.5 129.15 1 102.1 102.14/102.08 2 129.7 116.34 2 74.4 74.40/74.33 3 115.0 144.93 3 78.9 78.89/78.94 4 155.6 143.50 4 69.1 69.07/69.10 5 115.0 115.47 5 73.1 73.07/73.00 6 129.7 119.49 6 68.0 68.01/68.08 α, (7) 70.1 70.23 Rha β, (8) 34.7 34.96 1 101.2 101.20
Ester 2 70.4 70.45 1 125.3 124.97/125.12 3 70.3 70.33 2 114.7 130.31/133.01 4 71.6 71.61/71.68 3 145.6 115.79/114.84 5 68.7 68.73/68.67 4 148.8 160.02/159.05 6 18.1 18.08/17.96 5 115.8 115.79/114.84 Glc′ 6 121.5 130.31/133.01 1 103.3 103.31?α(7) 113.2 113.52/114.29 2 73.4 73.40?β(8) 145.9 145.44/145.35 3 76.5 76.55 CO 166.0 166.05/164.86 4 69.9 69.89
5 76.8 76.82
6 61.0 60.94 table 4. compounds 3 1HNMR and 13(δ, solvent are MeOH-d to the chemical displacement value of CNMR 4) sequence number hydrogen atom carbon atom Aglycone 1-----133.60/133.54 2 6.84 (d, 1.6) 6.85 (d, 1.6) 114.68/114.77 3----146.25/146.23 4-----146.08/146.01 5 6.73 (d, 8.1) 6.73 (d, 8.1) 116.20/116.17 6 6.71 (br.d, 8.1) 6.71 (br.d, 8.1) 119.01/119.13 α (8) 3.59,3.93 3.80,3.84 76.92/77.53 β (7) 4.75 4.73 74.11/73.86Ester 1--127.64 2 7.05 (br.s) 115.28 3--146.84 4---149.85 5 6.77 (d, 8.2) 116.52 6 6.96 (br.d, 8.2) 123.27 α (8) 6.27 (d, 15.8) 114.62 β (7) 7.59 (d, 15.8) 148.27 CO---168.45/168.37 Glc 1 4.43 (d, 8.0) 4.44 (d, 8.0) 104.63/104.51 2 3.46 (t, 8.7) 76.34/76.05 3 3.84 (t, 9.4) 81.29/81.37 4 5.03 (t, 9.7) 4.99 (t, 9.7) 70.45/70.56 5 3.80 74.67/74.75,6 3.62 69.41/69.51
3.93 Rha 1 5.20 (br.s) 5.19 (br.s) 102.95/103.02 2 3.92 72.34 3 3.57 72.05 4 3.28 73.75 5 3.55 70.45 6 1.08 (d; 6.2) 18.43 Glc ', 1 4.26 (d; 7.7) 4.29 (d; 7.7) 104.65/104.63 2 3.18 75.07/75.11 3 3.33 77.78/77.71 4 3.26 71.44 5 3.22 77.92/77.87 6 3.61,3.81 62.61/62.58 table 5. compounds 41HNMR and 13(δ, solvent are MeOH-d to the CNMR value 4)
Sequence number hydrogen atom carbon atom
Aglycone
1 -- 133.2
2 6.67(d，2.0) 117.1
3 -- 147.3
4 -- 147.5
5 6.81(d，8.5) 112.8
6 6.63(dd，8.5，2.0) 121.1
α(8) 3.66，4.09 71.8
β(7) 2.72(m) 36.3
OMe 3.81(s) 56.5
Ester
1 -- 127.4
2 7.03(br.s) 115.1
3 -- 147.0
4 -- 150.3
5 6.76(d，8.5) 116.5
6 6.94(br.d，8.5) 123.3
α(8) 6.26(d，16.0) 114.4
β(7) 7.59(d，16.0) 148.2
CO -- 168.1
Glc
1 4.35(d，8.0) 101.7
2 4.87(t，9.5) 75.1
3 4.01(t，9.5) 80.5
4 4.99(t，9.5) 70.8
5 3.75 76.2
6 3.49，3.67 62.2
OAc
CH 3 1.98(s) 20.9
CO -- 171.4
Rha
1 4.79(br.s) 103.3
2 3.63 72.6
3 3.52 71.6
4 3.25(t，9.0) 73.6
5 3.50 70.6
6 1.06(d，6.0) 18.5
Table 6. compound 5 1HNMR, 13(δ, solvent are MeOH-d to the CNMR value 4) sequence number carbon atom hydrogen atom and long-range relevant hydrogen atom Aglycone 1 131.8--the A-5 of carbon; A-α 2 113.9 6.77 (1H, br.s) A-6 3 148.7--A-2; A-5; A-OMe 4 145.8--A-2; A-5; A-6 5 116.0 6.69 (1H, br.d, 8.0)--6 122.3 6.63 (1H, br.d, 8.0) A-2 α 71.9 4.10 (1H, m); 3.52 (1H, m) G-1 β 36.6 2.76 (2H, m) A-2 OMe 56.3 3.85 (3H, s)--Ester 1 127.6--E-5; E-β 2 115.2 7.03 (1H, br.s) E-6; E-γ 3 146.7--E-2; E-5 4 149.6--E-2; E-6 5 116.5 6.77 (1H, br.d, 7.5)--6 123.2 6.94 (1H, br.d, 7.5) E-2; E-γ α 168.1--E-γ β 114.5 6.26 (1H, d, 15.9)--γ 148.2 7.59 (1H, d, 15.9) E-2; E-6 Glc. 1 101.8 4.53 (1H, d, 8.0) G-2 2 75.1 4.84 (1H) G-3 3 80.5 4.00 (1H, t, 9.3) G-2; R-1 4 70.6 4.98 (1H, t, 9.3) G-3 5 76.1 3.59 (1H, m)--6 62.2 3.62 (1H, m); 3.53 (1H, m)--OAc CH 320.8 1.92 (3H, s)--CO 171.3--OAc-CH 3Rha. 1 103.3 4.79 (1H, s) G-3 2 72.6 3.64 (1H, m)--3 71.9 3.65 (1H, m)--4 73.6 3.25 (1H, t, 9.5) R-6 5 70.8 3.53 (br.d) R-1; R-6 6 18.5 1.06 (3H, d, 6.1)--
Table 7. compound 6 1HNMR and 13(δ, solvent are DMSO-d to the CNMR value 6) sequence number carbon atom hydrogen atom and the long-range relevant hydrogen atom Aglycone of carbon
1 128.9 -- A-3；A-β；A-α
2 129.9 6.97(2H，d，8.1) A-β；A-6
3 115.1 6.64(2H，d，8.1) A-5
4 155.7 -- A-2；A-6；A-3；A-5
5 115.1 6.64(2H，d，8.1) A-3
6 129.9 6.97(2H，d，8.1) A-2；A-β
α 70.0 3.55(m)；3.90(1H，m) G-1；A-β
β 34.5 2.65(2H，m) A-2；A-6 Ester
1 125.5 -- E-5；E-β；E-γ
2 114.7 7.02(1H，s) E-γ；E-6
3 145.7 -- E-5
4 148.8 -- E-2；E-6
5 115.9 6.75(1H，d，7.0) --
6 121.7 6.96(1H，d，7.0) E-γ；E-2
α 165.8 -- E-γ；E-β；G-4
β 113.4 6.21(1H，d，16.0) E-γ
γ 146.1 7.46(1H，d，16.0) E-6 Glc.
1 99.3 4.60(1H，d，7.5) G-2；A-α
2 73.6 4.68(1H，t，9.0) G-3
3 78.2 3.95(1H，t，9.5) R-1；G-2；G-4
4 69.0 4.80(1H，t，9.5) G-3
5 74.6 3.58(1H，m) G-6；G-4
6 60.5 3.33(1H，m)； G-4
3.39(1H，m) OAc CH 3 20.7 1.95(3H，s) -- CO 169.3 -- G-2；CO-CH 3 Rha.
1 102.1 4.59(1H，br.s) G-3
2 70.9 3.35(1H，br.s) R-1
3 70.2 3.20(1H，br.d，10.0) R-2；R-4
4 71.5 3.06(1H，t，9.5) R-2；R-3
5 69.4 3.30(1H，m) R-1
6 18.3 0.90(3H，d，6.0) R-4
Table 8. compound 7 1HNMR and 13(δ, solvent are MeOH-d to the CNMR value 4) sequence number carbon atom hydrogen atom and long-range relevant hydrogen atom Aglycone 1 129.3--the A-5 of carbon; A-β; A-α 2 116.3 6.46 (1H, br.s) A-6 3 145.0--A-2; A-5; A-6 4 143.6--A-2; A-5; A-6 5 115.4 6.49 (1H, br.d, 8.1) A-6 6 119.5 6.31 (1H, br.d, 8.1) A-2 α 69.9 3.41 (1H, d, 12.3); 3.72 (1H, m) A-2; A-β; G-1 β 34.8 2.49 (2H, m) A-6; A-2; A-α Ester 1 125.1--E-β; E-γ; E-3; E-5 2 130.4 7.45 (1H, d, 7.8) E-6 3 115.8 6.69 (1H, d, 7.8) E-5; E-2; E-6 4 160.0--E-3; E-5; E-2; E-6 5 115.8 6.69 (1H, d, 7.8) E-3; E-6; E-2 6 130.4 7.45 (1H, d, 7.8) E-2 α 166.6--G-6; E-β; E-γ β 114.0 6.35 (1H, d, 16.0) E-γ γ 145.0 7.46 (1H, d, 16.0) E-2; E-6 Glc. 1 99.5 4.45 (1H, d, 8.4) G-2; G-5; A-α 2 73.3 4.55 (1H, t, 9.0) G-3 3 79.5 3.52 (1H, t, 9.3) R-1; R-2; G-2; G-4 4 68.8 3.25 (1H, t, 9.0) R-1; G-2; G-3; G-6 5 73.8 3.47 (1H, m) G-1; G-4; G-6 6 63.1 4.29 (1H, d, 11.4); 4.13 (1H, m) G-4 OAc CH 320.6 1.88 (3H, s)--CO 169.2--G-2;-CH 3Rha. 1 101.3 4.55 (1H, br.s) G-3; R-5 2 70.5 3.29 (1H, br.s) R-1; R-3 3 70.7 3.39 (1H, br.d, 10.5) R-4; R-5 4 71.9 3.08 (1H, t, 9.0) R-2; R-3; R-5 5 68.7 3.70 (1H, m) R-1; R-4; R-3 6 17.8 1.00 (3H, d, 6.3) R-5; R-4
The invention effect: the present invention utilizes multiple means, comprises silica gel column chromatography, macroporous absorbent resin, sephadex LH-20 column chromatography and preparative high performance liquid chromatography etc. separate from three kinds of Cistanche deserticola plants and prepare 7 Individual new benzyl carbinol glycosides compounds shows through preliminary determination of activity, and it is thin that this compounds has certain anti-nerve Born of the same parents' apoptosis effect, thereby for furtheing investigate from now on these activated monomer compounds of exploitation and being used for clinical having established Material base.

Claims (7)

1, a kind of benzyl carbinol glycosides compounds 1 (pipe flower glycosides A, cistantubuloside A)
Structural formula 1
2, a kind of benzyl carbinol glycosides compounds 2 (pipe flower glycosides B 1/ B 2, cistantubulosides B 1/ B 2),
Structural formula 2
3, a kind of benzyl carbinol glycosides compounds 3 (pipe flower glycosides C 1/ C 2, cistantubulosides C 1/ C 2),
Structural formula 3
Figure A0211764100031
4, a kind of benzyl carbinol glycosides compounds 4 (Cistansinenside A, cistansinenside A),
Structural formula 4
Figure A0211764100032
5, a kind of benzyl carbinol glycosides compounds 5 (2'-acetylcistanoside C, 2 '-acetylcistanoside C),
Structural formula 5
Figure A0211764100033
6, a kind of benzyl carbinol glycosides compounds 6 (2'-acetylosmanthuside, 2 '-acetylosmanthuside),
Structural formula 6
Figure A0211764100041
7, a kind of benzyl carbinol glycosides compounds 7 (Isotubuloside E, isotubuloside E),
Structural formula 7
Figure A0211764100042
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Cited By (11)

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Publication number Priority date Publication date Assignee Title
WO2005028491A1 (en) * 2003-09-19 2005-03-31 Shanghai Yao Gang Biological Technology Co., Ltd. Epimeredi glycoside a, the formulation containing thereof and their preparation method
WO2008046258A1 (en) * 2006-10-17 2008-04-24 Hailong Wang Cosmetic composition and preparation method and use thereof
WO2008116391A1 (en) * 2007-03-26 2008-10-02 Sinphar Tian-Li Pharmaceutical Co., Ltd. (Hangzhou) The neuroblast proliferation promoter and the neurite outgrowth promoter
CN101129391B (en) * 2007-09-12 2010-09-29 新疆维吾尔自治区中药民族药研究所 Medicament for eliminating OH free radical
CN101271089B (en) * 2005-05-12 2012-07-25 新疆医科大学 Method for identifying allantoin in Cistanche plant variety
CN103622980A (en) * 2013-12-12 2014-03-12 宁夏医科大学 Application of cistanche phenylethanoid glycoside compound to preparation of drugs for treating osteoporosis and drug composition containing cistanche phenylethanoid glycoside compound
CN104262414A (en) * 2014-09-17 2015-01-07 中国科学院过程工程研究所 Method for preparing phenylethanoid glycoside, mannitol, oligosaccharide syrup and polysaccharide from broomrape
CN105628798A (en) * 2014-10-29 2016-06-01 江苏康缘药业股份有限公司 Cistanchis glycoside capsule fingerprint detection method
CN107727763A (en) * 2017-09-30 2018-02-23 宁夏医科大学 Seven kinds of benzyl carbinol glycosides composition fast qualitatives and quantitative detecting method in saline cistanche medicinal material
CN111574573A (en) * 2020-05-21 2020-08-25 深圳市人民医院 Fifteen phenylethanoid glycoside compounds and separation and purification method and application thereof
CN112940055A (en) * 2021-01-26 2021-06-11 上海中医药大学 Phenylethanoid glycoside compound extracted from Caryopteris clandonensis and preparation method and medical application thereof

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005028491A1 (en) * 2003-09-19 2005-03-31 Shanghai Yao Gang Biological Technology Co., Ltd. Epimeredi glycoside a, the formulation containing thereof and their preparation method
CN101271089B (en) * 2005-05-12 2012-07-25 新疆医科大学 Method for identifying allantoin in Cistanche plant variety
WO2008046258A1 (en) * 2006-10-17 2008-04-24 Hailong Wang Cosmetic composition and preparation method and use thereof
WO2008116391A1 (en) * 2007-03-26 2008-10-02 Sinphar Tian-Li Pharmaceutical Co., Ltd. (Hangzhou) The neuroblast proliferation promoter and the neurite outgrowth promoter
CN101129391B (en) * 2007-09-12 2010-09-29 新疆维吾尔自治区中药民族药研究所 Medicament for eliminating OH free radical
CN103622980A (en) * 2013-12-12 2014-03-12 宁夏医科大学 Application of cistanche phenylethanoid glycoside compound to preparation of drugs for treating osteoporosis and drug composition containing cistanche phenylethanoid glycoside compound
CN104262414A (en) * 2014-09-17 2015-01-07 中国科学院过程工程研究所 Method for preparing phenylethanoid glycoside, mannitol, oligosaccharide syrup and polysaccharide from broomrape
CN104262414B (en) * 2014-09-17 2017-03-22 中国科学院过程工程研究所 Method for preparing phenylethanoid glycoside, mannitol, oligosaccharide syrup and polysaccharide from broomrape
CN105628798A (en) * 2014-10-29 2016-06-01 江苏康缘药业股份有限公司 Cistanchis glycoside capsule fingerprint detection method
CN107727763A (en) * 2017-09-30 2018-02-23 宁夏医科大学 Seven kinds of benzyl carbinol glycosides composition fast qualitatives and quantitative detecting method in saline cistanche medicinal material
CN107727763B (en) * 2017-09-30 2022-05-24 宁夏医科大学 Quick qualitative and quantitative detection method for seven phenylethanoid glycoside components in cistanche deserticola medicinal material
CN111574573A (en) * 2020-05-21 2020-08-25 深圳市人民医院 Fifteen phenylethanoid glycoside compounds and separation and purification method and application thereof
CN112940055A (en) * 2021-01-26 2021-06-11 上海中医药大学 Phenylethanoid glycoside compound extracted from Caryopteris clandonensis and preparation method and medical application thereof

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