CN102531904A - Novel gentianic acid derivative 2-hydroxy-5-substituted long-chain fat acyloxymethyl benzoates, preparation method for novel gentianic acid derivative and application of novel gentianic acid derivative - Google Patents
Novel gentianic acid derivative 2-hydroxy-5-substituted long-chain fat acyloxymethyl benzoates, preparation method for novel gentianic acid derivative and application of novel gentianic acid derivative Download PDFInfo
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Abstract
The invention discloses a novel gentianic acid derivative, namely 2-hydroxy-5-substituted long-chain fat acyloxymethyl benzoates. The structural formula of the derivative is shown in the specification; and in the structural formula, R is one of linoleic acid, myristic acid, palmitic acid, oleic acid, arachic acid, stearic acid, erucic acid, behenic acid and ricinoleic cid in long-chain fatty acid. The invention also discloses application of the novel gentianic acid derivative, namely the 2-hydroxy-5-substituted long-chain fat acyloxymethyl benzoates to the field of skin whitening. The derivative is low in toxicity and high in stability, has better pharmacological activity, and has a good whitening effect.
Description
Technical field
The present invention relates to the skin whitening field, relate in particular to a kind of novel gentisinic acid verivate 2-hydroxyl-5-and replace long-chain fat acyloxy oil of Niobe class and preparation method thereof and new purposes.
Background technology
Makeup both domestic and external enterprise all explore, the raw material of research and development Pear Power effect of dispelling spots, whitening cosmetics is the best-selling product in market, Asia always.According to statistics, have 70% women to think that one of the biggest obstacle of beauty treatment is the formation of facial freckle, chloasma, senile plaque approximately, they belong to common Pigmented tetter, influence appearance, cause serious psychological pressure to the patient.Present whitening and speckle dispelling raw material is all having many deficiencies aspect security and the effect property, be prone to decompose such as the toxicity of quinhydrones, vitamins C etc.
Gentisinic acid is 2, and 5-resorcylic acid (2,5-dihydroxybenzoic acid) is a kind of Radix Gentianae extract, and it is a kind of verivate of quinhydrones, mainly has the effect of restraint of tyrosinase isoreactivity, and its structural formula is as follows:
Resorcinol; Be that (Hydroquinone HQ) is traditional whitening and speckle dispelling composition to quinhydrones, but because safety-problems; Spell out in the cosmetic composition review summary of CTFA version in 2000; Forbid that quinhydrones is used for the presence makeup, non-resident makeup consumption is less than 1 %, so quinhydrones is improper whitening agent as makeup.And gentisinic acid can use quinhydrones, Whitfield's ointment etc. for feedstock production, and its many verivates all show good biological activity, as whiten, anti-inflammatory, analgesia, analgesic etc.The gentisinic acid methyl esters is 2; The 5-methyl dihydroxy benzoate is the alkyl esters verivate of gentisinic acid, and tyrosine oxidase is had the better inhibited effect; The initial synthesis phase of melanocytic melanocyte is had restraining effect in concentration during less than 60mg/ml, and pair cell toxic action and mutagenesis are less.One of focus of the research and development that to develop safer more effective skin-whitening agents be current makeup, therefore, synthesizing new gentisinic acid verivate has extremely important and actual significance.
Summary of the invention
To the problem that exists in the above-mentioned prior art, the object of the invention just is to provide a kind of novel gentisinic acid verivate 2-hydroxyl-5-to replace long-chain fat acyloxy oil of Niobe class and new purposes thereof, and toxicity is little, stability is high and have better pharmacologically active.
Another object of the present invention is to provide a kind of novel gentisinic acid verivate 2-hydroxyl-5-to replace the preparation method of long-chain fat acyloxy oil of Niobe class.
To achieve these goals, the technical scheme that the present invention adopts is such: novel gentisinic acid verivate 2-hydroxyl-5-replaces long-chain fat acyloxy oil of Niobe class, and its structural formula is:
In the said structural formula, R is a kind of in linolic acid in the longer chain fatty acid, TETRADECONIC ACID, palmitinic acid, oleic acid, eicosanoic acid, Triple Pressed Stearic Acid, erucic acid, mountain Yu's acid and the ricinolic acid.
Novel gentisinic acid verivate 2-hydroxyl-5-replaces long-chain fat acyloxy oil of Niobe class, is applied to the skin whitening field.
Novel gentisinic acid verivate 2-hydroxyl-5-replaces the preparation method of long-chain fat acyloxy oil of Niobe class; Comprise gentisinic acid methyl esters, longer chain fatty acid, N, N'-NSC 57182 (DCC), 4-Dimethylamino pyridine (DMAP) and anhydrous methylene chloride;
The gentisinic acid methyl esters is 1:1 ~ 2 with the ratio of the mole number of longer chain fatty acid;
Under 20 ~ 25 ℃; Add the gentianic acid methyl esters under the magnetic stirring apparatus condition; Be solution again with the anhydrous methylene chloride; With DCC is the ester condensation agent; DMAP is a catalyst, and adds LCFA, under 20 ~ 30 ℃ of conditions more than the stirring reaction 5h; Reacted the back and filtered, crude product obtains 2-hydroxyl-5-through the silica gel chromatographic column purifies and separates and replaces long-chain fat acyloxy methyl benzoate;
Its reaction process is:
In the above-mentioned reaction formula,
1: the gentisinic acid methyl esters
2a:2-hydroxyl-5-(Z-9,12-18 carbon diene acyloxy) oil of Niobe
2b:2-hydroxyl-5-n-tetradecane acyloxy oil of Niobe
2c:2-hydroxyl-5-NSC 62789 acyloxy oil of Niobe
2d:2-hydroxyl-5-(Z-9-vaccenic acid acyloxy) oil of Niobe
2e:2-hydroxyl-5-n-hexadecane acyloxy oil of Niobe
2f:2-hydroxyl-5-Octadecane acyloxy oil of Niobe
2g:2-hydroxyl-5-(Z-13-two dodecylene acyloxy) oil of Niobe
2h:2-hydroxyl-5-n-docosane acyloxy oil of Niobe
2i:2-hydroxyl-5-[[R-(Z)]-12-hydroxyl-9-vaccenic acid acyloxy] oil of Niobe.
Compared with prior art, the invention has the advantages that:
1, novel gentisinic acid verivate according to the invention is compared with VitC with the gentisinic acid methyl esters; It is active that majority of compounds has stronger restraint of tyrosinase; Thereby be active pharmaceutical ingredients with it, can develop the multiple whitening medicaments of better efficacy, have obvious social and economic benefit.
2, the method for the invention operational path is very simple, and cost is lower, and the yield of product is higher, can be suitable for industriallization and enlarge the needs of producing.
Embodiment
Embodiment 1: novel gentisinic acid verivate 2-hydroxyl-5-replaces long-chain fat acyloxy oil of Niobe class, and its structural formula is:
In the said structural formula, R is a kind of in linolic acid in the longer chain fatty acid, TETRADECONIC ACID, palmitinic acid, oleic acid, eicosanoic acid, Triple Pressed Stearic Acid, erucic acid, mountain Yu's acid and the ricinolic acid.
Novel gentisinic acid verivate 2-hydroxyl-5-replaces long-chain fat acyloxy oil of Niobe class, is applied to the skin whitening field.
Novel gentisinic acid verivate 2-hydroxyl-5-replaces the preparation method of long-chain fat acyloxy oil of Niobe class, comprises gentisinic acid methyl esters, longer chain fatty acid, DCC, DMAP and anhydrous methylene chloride;
The gentisinic acid methyl esters is 1:1 ~ 2 with the ratio of the mole number of longer chain fatty acid;
Under 20 ~ 25 ℃; Add the gentianic acid methyl esters under the magnetic stirring apparatus condition; Be solution again with the anhydrous methylene chloride; With DCC is the ester condensation agent; DMAP is a catalyst, and adds LCFA, under 20 ~ 30 ℃ of conditions more than the stirring reaction 5h; Reacted the back and filtered, crude product obtains 2-hydroxyl-5-through the silica gel chromatographic column purifies and separates and replaces long-chain fat acyloxy methyl benzoate;
Its reaction process is:
In the above-mentioned reaction formula,
1: the gentisinic acid methyl esters
2a:2-hydroxyl-5-(Z-9,12-18 carbon diene acyloxy) oil of Niobe
2b:2-hydroxyl-5-n-tetradecane acyloxy oil of Niobe
2c:2-hydroxyl-5-NSC 62789 acyloxy oil of Niobe
2d:2-hydroxyl-5-(Z-9-vaccenic acid acyloxy) oil of Niobe
2e:2-hydroxyl-5-n-hexadecane acyloxy oil of Niobe
2f:2-hydroxyl-5-Octadecane acyloxy oil of Niobe
2g:2-hydroxyl-5-(Z-13-two dodecylene acyloxy) oil of Niobe
2h:2-hydroxyl-5-n-docosane acyloxy oil of Niobe
2i:2-hydroxyl-5-[[R-(Z)]-12-hydroxyl-9-vaccenic acid acyloxy] oil of Niobe.
Embodiment 2: present embodiment prepares 2-hydroxyl-5-(Z-9,12-18 carbon diene) acyloxy oil of Niobe (being called for short 2a), and its structural formula is following:
The process step of present embodiment is following:
2-hydroxyl-5-(Z-9,12-18 carbon diene) acyloxy oil of Niobe (is called for short
2a) preparation
Get the pure article of gentisinic acid methyl esters of 100mg (0.60mmol), be dissolved in 10mlCH
2Cl
2Solution adds 0.03gDMAP then successively, the linolic acid of 0.31g (0.72mmol), and the stirring at room reaction is after 5 minutes; Add 0.20 gDCC, continue the stirring at room reaction, the TLC monitoring reaction; After reacting completely, filter, filtrate decompression concentrates; With thick product through column chromatography (sherwood oil: ETHYLE ACETATE=8:1) pale yellow oily liquid body 2-hydroxyl-5-(Z-9,12-18 carbon diene) acyloxy oil of Niobe, productive rate 95%;
1HNMR (400MHz, CDCl
3) δ: 0.89 (t, 3H, CH
3), 1.21 ~ 1.39 (m, 6H, CH
2), 1.48 ~ 1.65 (m, 8H, CH
2), 1.48 ~ 1.56 (m, 8H, CH
2), 1.74 (m, 2H, CH
2), 2.02 ~ 2.07 (q,
J=6.4Hz, 2H, CH
2), 2.31 ~ 2.36 (q,
J=7.6Hz, 2H, CH
2), 2.54 (t, 2H, CH
2), 2.78 (t, 2H, CH
2), (3.94 (s, 3H, COOCH
3), 5.30 ~ 5.42 (m, 4H, CH=CH), 6.98 (d,
J=8.8Hz, 1H, PhH), 7.16 ~ 7.19 (q,
J=2.8Hz, 1H, PhH), 7.56 (d,
J=2.8Hz, 1H, PhH), 10.65 (s, 1H, OH); IR (KBr,
ν, cm
-1): 3198,2927,2856,1710,1621,1486,1442,1338,1285,1211,1128,1082,978,832,790,722; HRMS (ESI) calcd for C
26H
38O
5[M+H]
+431.2792 found 431.3631; [M+Na]
+453.2611, found 453.2494.
Embodiment 3: present embodiment prepares the positive myristoyl aminobenzoic acid of 2-hydroxyl-5-methyl esters (being called for short 2b), and its structural formula is following:
The process step of present embodiment is following:
The positive myristoyl aminobenzoic acid of 2-hydroxyl-5-methyl esters (is called for short
2b) preparation
Get the pure article of gentisinic acid methyl esters of 0.10g (0.60mmol), be dissolved in 10mlCH
2Cl
2Solution adds 0.03gDMAP then successively, the tetradecanoic acid of 0.16g (0.72mmol); The stirring at room reaction added 0.20 gDCC after 5 minutes, continued the stirring at room reaction; The TLC monitoring reaction after reacting completely, filters; Filtrate decompression concentrates, with thick product through column chromatography (sherwood oil: ETHYLE ACETATE=8:1) the positive myristoyl aminobenzoic acid of white solid 2-hydroxyl-5-methyl esters, productive rate 98%; M.p.42 ~ 43 ℃;
1HNMR (400MHz, CDCl
3) δ: 0.88 (t, 3H, CH
3), 0.98 ~ 1.41 (m, 20H, CH
2), 1.74 (m, 2H, CH
2), 2.53 (t, 2H, OCOCH
2), 3.94 (s, 3H, COOCH
3), 6.98 (d,
J=8.8Hz, 1H, PhH), 7.16 (d,
J=2.8Hz, 1H, PhH), 7.55 (d,
J=2.8Hz, 1H, PhH), 10.65 (s, 1H, OH); IR (KBr,
ν, cm
-1): 3233,2915,2850,1756,1674,1620,1437,1203,1148,1091,983,907,830,776,717,666; HRMS (ESI) calcd for C
22H
34O
5[M+H]
+379.2479 found 379.2453; [M+Na]
+401.2298, found 401.2263.
Embodiment: 4: present embodiment prepares 2-hydroxyl-5-NSC 62789 acyloxy oil of Niobe (being called for short 2c), and its structural formula is following:
The process step of present embodiment is following:
2-hydroxyl-5-NSC 62789 acyloxy oil of Niobe (is called for short
2c) preparation
Get the pure article of gentisinic acid methyl esters of 0.10g (0.60mmol), be dissolved in 10mlCH
2Cl
2Solution adds 0.03gDMAP then successively, the eicosanoic acid of 0.22g (0.72mmol); The stirring at room reaction added 0.20 gDCC after 5 minutes, continued the stirring at room reaction; The TLC monitoring reaction after reacting completely, filters; Filtrate decompression concentrates, with thick product through column chromatography (sherwood oil: ETHYLE ACETATE=8:1) white solid 2-hydroxyl-5-NSC 62789 acyloxy oil of Niobe, productive rate 98%; M.p.52 ~ 54 ℃;
1HNMR (400MHz, CDCl
3) δ: 0.88 (t, 3H, CH
3), 1.26 ~ 1.41 (m, 20H, CH
2), 1.74 (m, 2H, CH
2), 2.53 (t, 2H, OCOCH
2), 3.94 (s, 3H, COOCH
3), 6.98 (d,
J=8.8Hz, 1H, PhH), 7.16 ~ 7.19 (q,
J=2.8Hz, 1H, PhH), 7.55 (d,
J=2.8Hz, 1H, PhH), 10.65 (s, 1H, OH); IR (KBr,
ν, cm
-1): 3233,2916,2850,1756,1676,1621,1489,1439,1335,1204,1149,1090,983,907,830,776,717,665; HRMS (ESI) calcd for C
28H
46O
5[M+H]
+463.3418 found 463.3344; [M+Na]
+485.3237, found485.3152.
Embodiment: 5: present embodiment prepares 2-hydroxyl-5-(Z-9-vaccenic acid) acyloxy oil of Niobe (being called for short 2d), and its structural formula is following:
The process step of present embodiment is following:
2-hydroxyl-5-(Z-9-vaccenic acid) acyloxy oil of Niobe (being called for short 2d):
Get the pure article of gentisinic acid methyl esters of 0.10g (0.60mmol), be dissolved in 10mlCH
2Cl
2Solution adds 0.03gDMAP then successively, the oleic acid of 0.31g (0.72mmol); The stirring at room reaction added 0.20 gDCC after 5 minutes, continued the stirring at room reaction; The TLC monitoring reaction after reacting completely, filters; Filtrate decompression concentrates, with thick product through column chromatography (sherwood oil: ETHYLE ACETATE=8:1) pale yellow oily liquid body 2-hydroxyl-5-(Z-9-vaccenic acid) acyloxy oil of Niobe, productive rate 97%;
1HNMR (400MHz, CDCl
3) δ: 0.89 (t, 3H, CH
3), 1.26 ~ 1.40 (m, 20H, CH
2), 1.74 (m, 2H, CH
2), 2.53 (t, 2H, OCOCH
2), 3.94 (s, 3H, COOCH
3), 5.34 ~ 5.39 (m, 2H, CH=CH), 6.98 (d,
J=9.2Hz, 1H, PhH), 7.16 ~ 7.19 (q,
J=2.8Hz, 1H, PhH), 7.55 (d,
J=2.8Hz, 1H, PhH), 10.65 (s, 1H, OH); IR (KBr,
ν, cm
-1): 3197,2924,1763,1684,1621,1485,1442,1339,1286,1211,1129,976,935,832,790,719; HRMS (ESI) calcd for C
26H
40O
5[M+H]
+433.2949 found 433.2918; [M+Na]
+455.2768 found 455.2714; [M+K]
+471.2507, found 471.2486.
Embodiment: 6: present embodiment prepares 2-hydroxyl-5-n-hexadecane acyloxy oil of Niobe (being called for short 2e), and its structural formula is following:
The process step of present embodiment is following:
2-hydroxyl-5-n-hexadecane acyloxy oil of Niobe (being called for short 2e) preparation
Get the pure article of gentisinic acid methyl esters of 0.10g (0.60mmol), be dissolved in 10mlCH
2Cl
2Solution adds 0.03gDMAP then successively, the palmitinic acid of 0.29g (0.72mmol), and the stirring at room reaction is after 5 minutes; Add 0.20 gDCC, continue the stirring at room reaction, the TLC monitoring reaction; After reacting completely, filter, filtrate decompression concentrates; With thick product through column chromatography (sherwood oil: ETHYLE ACETATE=8:1) white solid 2-hydroxyl-5-n-hexadecane acyloxy oil of Niobe, productive rate 96%, m.p.47 ~ 48 ℃;
1HNMR (400MHz, CDCl
3) δ: 0.72 (t, 3H, CH
3), 1.26 ~ 1.40 (m, 20H, CH
2), 1.74 (m, 2H, CH
2), 2.53 (t, 2H, OCOCH
2), 3.94 (s, 3H, COOCH
3), 5.34 ~ 5.39 (m, 2H, CH=CH), 6.98 (d,
J=9.2Hz, 1H, PhH), 7.16 ~ 7.19 (q,
J=2.8Hz, 1H, PhH), 7.55 (d,
J=2.8Hz, 1H, PhH), 10.65 (s, 1H, OH); IR (KBr,
ν, cm
-1): 3233,2980,2914,2873,1744,1680,1615,1491,1428,1385,1278,1240,1194,1090,1017,840,787,750,701; HRMS (ESI) calcd for C
24H
38O
5[M+H]
+407.2792 found 407.2734; [M+Na]
+429.2611 found 429.2543; [M+K]
+445.2351, found 445.2281.
Embodiment 7: present embodiment prepares 2-hydroxyl-5-Octadecane acyloxy oil of Niobe (being called for short 2f), and its structural formula is following:
The process step of present embodiment is following:
2-hydroxyl-5-Octadecane acyloxy oil of Niobe (being called for short 2f) preparation
Get the pure article of gentisinic acid methyl esters of 0.10g (0.60mmol), be dissolved in 10mlCH
2Cl
2Solution adds 0.03gDMAP then successively, the palmitinic acid of 0.31g (0.72mmol), and the stirring at room reaction is after 5 minutes; Add 0.20 gDCC, continue the stirring at room reaction, the TLC monitoring reaction; After reacting completely, filter, filtrate decompression concentrates; With thick product through column chromatography (sherwood oil: ETHYLE ACETATE=8:1) white solid 2-hydroxyl-5-Octadecane acyloxy oil of Niobe, productive rate 97%, m.p.28 ~ 29 ℃;
1HNMR (400MHz, CDCl
3) δ: 0.88 (t, 3H, CH
3), 1.24 ~ 1.42 (m, 28H, CH
2), 1.74 (m, 2H, CH
2), 2.54 (t, 2H, OCOCH
2), 3.94 (s, 3H, COOCH
3), 6.98 (d,
J=9.2Hz, 1H, PhH), 7.16 ~ 7.19 (q,
J=2.8Hz, 1H, PhH), 7.55 (d,
J=2.8Hz, 1H, PhH), 10.66 (s, 1H, OH); IR (KBr,
ν, cm
-1): 3170,2917,2850,1737,1678,1618,1485,1468,1485,1458,1381,1341,1215,1144,1079,981,908,833,792,721; HRMS (ESI) calcd for C
26H
42O
5[M+H]
+435.3105 found 435.3085; [M+Na]
+457.2924, found 457.2882.
Embodiment 8: present embodiment prepares 2-hydroxyl-5-(Z-13-two dodecylenes) acyloxy oil of Niobe (being called for short 2g), and its structural formula is following:
The process step of present embodiment is following:
2-hydroxyl-5-(Z-13-two dodecylenes) acyloxy oil of Niobe (being called for short 2g) preparation
Get the pure article of gentisinic acid methyl esters of 0.10g (0.60mmol), be dissolved in 10mlCH
2Cl
2Solution adds 0.03gDMAP then successively, the erucic acid of 0.24g (0.72mmol); The stirring at room reaction added 0.20 gDCC after 5 minutes, continued the stirring at room reaction; The TLC monitoring reaction after reacting completely, filters; Filtrate decompression concentrates, with thick product through column chromatography (sherwood oil: ETHYLE ACETATE=8:1) white solid 2-hydroxyl-5-(Z-13-two dodecylenes) acyloxy oil of Niobe, productive rate 96%; M.p.21 ~ 22 ℃;
1HNMR (400MHz, CDCl
3) δ: 0.88 (t, 3H, CH
3), 1.28 ~ 1.40 (m, 28H, CH
2), 1.99 ~ 2.04 (q,
J=6Hz, 4H, CH
2), 1.74 (m, 2H, CH
2), 2.53 (t, 2H, OCOCH
2), 3.94 (s, 3H, COOCH
3), 5.31 ~ 5.39 (m, 2H, CH=CH), 6.98 (d,
J=8.8Hz, 1H, PhH), 7.16 ~ 7.19 (q,
J=2.8Hz, 1H, PhH), 7.55 (d,
J=2.8Hz, 1H, PhH), 10.65 (s, 1H, OH); IR (KBr,
ν, cm
-1): 3194,2925,2854,1763,1685,1485,1442,1338,1286,1211,1131,977,832,790,717; HRMS (ESI) calcd for C
30H
50O
5[M+H]
+491.3731 found 491.4467; [M+Na]
+513.3550 found 513.4299; [M+K]
+529.3290, found 529.4019.
Embodiment: 9: present embodiment prepares 2-hydroxyl-5-n-docosane acyloxy oil of Niobe (being called for short 2h), and its structural formula is following:
The process step of present embodiment is following:
2-hydroxyl-5-n-docosane acyloxy oil of Niobe (being called for short 2h) preparation
Get the pure article of gentisinic acid methyl esters of 0.10g (0.60mmol), be dissolved in 10mlCH
2Cl
2Solution adds 0.03gDMAP then successively, mountain Yu acid of 0.25g (0.72mmol); The stirring at room reaction added 0.20 gDCC after 5 minutes, continued the stirring at room reaction; The TLC monitoring reaction after reacting completely, filters; Filtrate decompression concentrates, with thick product through column chromatography (sherwood oil: ETHYLE ACETATE=8:1) white solid 2-hydroxyl-5-n-docosane acyloxy oil of Niobe, productive rate 99%; M.p.58 ~ 60 ℃;
1HNMR (400MHz, CDCl
3) δ: 0.88 (t, 3H, CH
3), 1.26 ~ 1.40 (m, 36H, CH
2), 1.74 (m, 2H, CH
2), 2.53 (t, 2H, OCOCH
2), 3.94 (s, 3H, COOCH
3), 6.98 (d,
J=8.8Hz, 1H, PhH), 7.16 ~ 7.19 (q,
J=2.8Hz, 1H, PhH), 7.55 (d,
J=2.8Hz, 1H, PhH), 10.65 (s, 1H, OH); IR (KBr,
ν, cm
-1): 3233,2916,2850,1756,1676,1621,1489,1472,1439,1204,1149,830,776,718,665; HRMS (ESI) calcd for C
30H
50O
5[M+H]
+491.3731 found 491.3707; [M+Na]
+513.3550 found 513.3529; [M+K]
+529.3290, found 529.3263.
Embodiment 10: present embodiment prepares 2-hydroxyl-5-[[R-(Z)]-12-hydroxyl-9-vaccenic acid] acyloxy oil of Niobe (being called for short 2i), and its structural formula is following:
The process step of present embodiment is following:
2-hydroxyl-5-[[R-(Z)]-12-hydroxyl-9-vaccenic acid] acyloxy oil of Niobe (being called for short 2i) preparation
Get the pure article of gentisinic acid methyl esters of 0.10g (0.60mmol), be dissolved in 10mlCH
2Cl
2Solution adds 0.03gDMAP then successively, mountain Yu acid of 0.22g (0.72mmol); The stirring at room reaction added 0.20 gDCC after 5 minutes, continued the stirring at room reaction; The TLC monitoring reaction after reacting completely, filters; Filtrate decompression concentrates, with thick product through column chromatography (sherwood oil: ETHYLE ACETATE=8:1) colourless oil liquid 2-hydroxyl-5-[[R-(Z)]-12-hydroxyl-9-vaccenic acid] acyloxy oil of Niobe, productive rate 95%;
1HNMR (400MHz, CDCl
3) δ: 0.88 (t, 3H, CH
3), 1.26 ~ 1.48 (m, 18H, CH
2), 1.74 (m, 2H, CH
2), 2.05 (t, 2H, CH
2), 2.21 (t, 2H, CH
2), 2.53 (t, 2H, OCOCH
2), 3.60 ~ 3.65 (m, 1H, CH), 3.94 (s, 3H, COOCH
3), 5.34 ~ 5.44 (m, 2H, CH=CH), 5.53 ~ 5.59 (m, 1H, OH), 6.98 (d,
J=8.8Hz, 1H, PhH), 7.16 ~ 7.19 (q,
J=2.8Hz, 1H, PhH), 7.55 (d,
J=2.8Hz, 1H, PhH), 10.65 (s, 1H, OH); IR (KBr,
ν, cm
-1): 3438,3197,2926,2855,1762,1685,1621,1485,1442,1338,1285,2924,1763,1684,1621,1485,1442,1339,1286,1211,1082,977,833,790,720; HRMS (ESI) calcd for C
26H
40O
6[M+H]
+449.2898 found 449.2831; [M+Na]
+471.2717 found 471.2637; [M+K]
+487.2456 found 487.2389.
Claims (3)
1. novel gentisinic acid verivate 2-hydroxyl-5-replaces long-chain fat acyloxy oil of Niobe class, and its structural formula is:
In the said structural formula, R is a kind of in linolic acid in the longer chain fatty acid, TETRADECONIC ACID, palmitinic acid, oleic acid, eicosanoic acid, Triple Pressed Stearic Acid, erucic acid, mountain Yu's acid and the ricinolic acid.
2. novel gentisinic acid verivate 2-hydroxyl-5-replaces long-chain fat acyloxy oil of Niobe class and preparation method thereof; It is characterized in that: comprise gentisinic acid methyl esters, longer chain fatty acid, N, N'-NSC 57182,4-Dimethylamino pyridine and anhydrous methylene chloride;
The gentisinic acid methyl esters is 1:1 ~ 2 with the ratio of the mole number of longer chain fatty acid;
Solvent is an anhydrous methylene chloride;
Under 20 ~ 25 ℃; Add the gentianic acid methyl esters under the magnetic stirring apparatus condition; Be solution again with the anhydrous methylene chloride; With DCC is the ester condensation agent; DMAP is a catalyst, and adds LCFA, under 20 ~ 30 ℃ of conditions more than the stirring reaction 5h; Reacted the back and filtered, crude product obtains 2-hydroxyl-5-through the silica gel chromatographic column purifies and separates and replaces long-chain fat acyloxy methyl benzoate;
Its reaction process is:
3. novel gentisinic acid verivate 2-hydroxyl as claimed in claim 1-5-replaces long-chain fat acyloxy oil of Niobe class, it is characterized in that: be applied to the skin whitening field.
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| CN2012100103846A CN102531904A (en) | 2012-01-13 | 2012-01-13 | Novel gentianic acid derivative 2-hydroxy-5-substituted long-chain fat acyloxymethyl benzoates, preparation method for novel gentianic acid derivative and application of novel gentianic acid derivative |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1219118A (en) * | 1996-05-02 | 1999-06-09 | 株式会社德库诺布耳 | Cosmetic |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1219118A (en) * | 1996-05-02 | 1999-06-09 | 株式会社德库诺布耳 | Cosmetic |
Non-Patent Citations (1)
| Title |
|---|
| 王伟等: "缩合剂1,3-二环己基碳二亚胺(DCC)在有机合成中的应用", 《化学试剂》 * |
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