GB2429455A - Synthesis of 5-(C15-25-alkyl/alkenyl)resorcinols via 8-(3,5-dihydroxyphenyl)octanal, the ozonolysis product of cardol, using Wittig & Grignard methodology - Google Patents
Synthesis of 5-(C15-25-alkyl/alkenyl)resorcinols via 8-(3,5-dihydroxyphenyl)octanal, the ozonolysis product of cardol, using Wittig & Grignard methodology Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
- C07C45/292—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups with chromium derivatives
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/001—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by modification in a side chain
- C07C37/003—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by modification in a side chain by hydrogenation of an unsaturated part
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/20—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms using aldehydes or ketones
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
- C07C39/08—Dihydroxy benzenes; Alkylated derivatives thereof
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- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/18—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with unsaturation outside the aromatic ring
- C07C39/19—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with unsaturation outside the aromatic ring containing carbon-to-carbon double bonds but no carbon-to-carbon triple bonds
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- C07—ORGANIC CHEMISTRY
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- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/40—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with ozone; by ozonolysis
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- C07C47/00—Compounds having —CHO groups
- C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
- C07C47/56—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing hydroxy groups
- C07C47/565—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing hydroxy groups all hydroxy groups bound to the ring
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/08—Preparation of carboxylic acids or their salts, halides or anhydrides from nitriles
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
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Abstract
Methods are disclosed for the synthesis of nature-identical 5-alkylresorcinols (C), 5-alkenylresorcinols and 5-alkadienylresorcinols (D), each having a C15-25 side chain, from an aldehyde intermediate (B) derived by the ozonolysis of cardol. Cardol is an abundant alkylresorcinolic component which comprises compounds of formula D (R is optionally unsaturated C6-alkyl). It is present in the natural product Anacardium occidentale (the cashew tree) and is present in its industrial decarboxylation product, the semi-synthetic technical cashew nutshell liquid (CNSL). The methods include the use of: <SL> <LI>(i) Wittig (or its modifications) or <LI>(ii) the combination of a Grignard chain extension and dehydration of the 8-(3,5-dihydroxyphenyl)octan-1-ol intermediate to yield the alkenyl/alkadienyl resorcinols and <LI>(iii) subsequent reduction of the C=C bond(s) to yield 5-alkylresorcinol. </SL> The nature-identical substances of this application occur notably in cereals (Graminae), wheat (Triticale species) and rye (Cereale secale). They are considered to confer health-promoting and some disease-preventive properties, and therefore may advantageously be used as a dietary supplement. The merits of the proposed route are the ready availability of the natural source for ozonolysis, the avoidance of protective group methodology and the requirement for availbale shorter chain reactants for the final synthetic steps.
Description
BRITISH PATENT SPECIFICATION
Synthesis of 5-alkyiresorcinols, (3,5-dihydroxy-n-alkylbenzenes) and 5alk(en)ylresorcinols, from aromatic aldehyde ozonolysis products obtained from unsaturated resorcinolic components of natural and semi-synthetic phenolic The major 5-n-alkylresorcinols and the minor 8(Z)-monoene and 8(Z),1 1(Z)-diene analogues are natural products which occur in Graminae (cereals) such as rye (Cereale secale)(A.Kozubek and J H P Tyman, Chem. and Phys. of Lipids,1 995, 78, 29-35; A Kozubek and R A Demel, Biochimica and Biophysica Ada, 1981, 642, 242) the bran fraction of wheat (Triricum aestivum) (E Wenkert, E -M Loeser, S N Mahapatra, F Schenker and E M Wilson, J Org. Chem, 1964, 29, 435) in barley grains (Hordeum distichon)(D E Briggs, Phytochemistry, 1974, 3, 987), and in whole grain cereals (J H P Tyman, Synthetic and Natural Phenols, Elsevier, 1996).
Several studies have shown that whole grain products possess healthpromoting properties, Thus, for example, protective effects have been demonstrated against cardiovascular disease, some forms of cancer and obesity (H Adlercreutz and A -M Linko, Brit. J Nutr. 2004, 92, 1-4; A Kozubek and J H P Tyman, Bioactive Phenolic Lipidc, in Studies in Natural Products Chemistry, Vol 30, part K, Elsevier, 2005; and PM Kris-Etherton and K D Hecker, Am. I Med., 2002,113, 71S). The levels of alkyiresorcinols and their monoenes and dienes in natural whole grains are however quite low. Thus, it is possible, if no proven undesirable side effects are manifested, that they could be employed as dietary supplements similar to the use of vitamin adjuncts in cereal products. This invention is concerned with an improved method for obtaining 5- alkyiresorcinols and their unsaturated monoene and diene analogues.
Description
In this novel approach, the synthesis of 5-alkyiresorcinols and their unsaturated analogues is proposed from the aromatic aldehyde intermediate, 8-(3,5- dihydroxyphenyl)octanal, resulting from ozonolysis of certain resorcinolic natural products. One compound from the first synthetic stage is a 3,5-dihydroxy- n- alk(en)ylbenzene and by reduction of this, a 3,5-dihydroxyphenyl-n- alkylbenzene (5- alkylresorcinol) results. The n-alkyl chain lengths of interest are from C15 to C25.
The raw material for ozonolysis is the phenolic lipid, cardol which is a component phenol of the natural resource, cashew nut shell liquid, Anacardium occidentale and of its industrial decarboxylation product, technical cashew nut shell liquid, both of which contain monoenr, diene and triene constituents all having unsaturation beginning at the 8position in the side chain (J H P Tyman, Synthertic and Natural Phenols, Elsevier, 1996) Analogous ozonolytic materials can also be used such as bilobol from Ginkgo biloba which also affords 8-(3,5-dihydroxyphenyl) octanal.
Ozonolysis has been employed almost entirely as an analytical technique for the cleavage of double bonds but the present invention represents a novel synthetic usage.
The next stage in this invention involves chain extension of the ozonolysis product by the Wittig, or by the Grignard reaction followed by dehydration to give a Z-monoene.
Reduction of the double bond in either reaction product affords, according to n-alkyl chain length of the intermediate used, a 5-n- alkyJresorcinol with a side chain in the t
I
range C1 to C25. Reaction of the same aldehyde with a bromo-(Z)-alkene affords a route to a dienoid side chain.
By contrast, current syntheses (A Kozubek and J II P lyman. Chem. Rev., 1999, 99,1- 29) of 5-alkyiresorcinols have started from expensive raw materials such as lithium and 3,5-dimethoxybenzaldehyde which are reacted with a 1- bromoalkane having a methylenic chain length C14 to C 22 to give a secondary alcohol. This is catalytically hydrogenolysed and the product then demethylated with, for example, the expensive reagent boron tribromide to give the required alkyiresorcinol. Alternatively, the same aldehyde can be reacted with a phosphonium salt in a Wittig reaction to give an alkene which is then reduced.
In another method 3,5-dimethoxyphenol has been employed (A Furstner and G Seidel, J Org.Chem., 1997, 62, 2332) and also 3,5-dimethoxybenzyl alcohol (U.
Azzena, G Dettori, M V. Idini, L. Pisano and G. Sechi, Appi. Organomet. Chem., 2003,17, 851) in both of which demethylation is necessary.
In the present invention cheap sodium ethoxide is used in the Wittig reaction and the demethylation stage is avoided.
The synthetic steps proposed in the present invention are shown in Scheme 1 Scheme I HO C15H31-n HO (CH2) 7CHO HO (CH2) 7CHCHR (1) (2) (3) 9R HO--' (CH2) 7CH=CHCH2CH=CHR
- III III
OH H
(4) (5) Reagents (Scheme 1): (i) 03, air,-78C; 112, PdJC, (ii) RCH2PPh3Bf, NaOEt, (iii)H2,Pd/C, (iv) RCH=CHCH2CH2PPh3Br, NaOEt The structure of the ozonolysis and reduction product (2) was confirmed by synthesis of its oxidation product the carboxylic acid (10) as shown in the following Scheme 2.
(10) was reduced to the related alconol.
Scheme 2, EnO CO2H BnO CO2Et BnO - CH2OH (6) (7) (8)
OH
BnO',1.CHO BnO...((L. (CH2) 60H (CH2) 1C02H y iv V Vi oa (9) (10) (11) Reagents(Scheme 2): (i) EtOH,H,(ii)LiAlH4, (iii) Py C1CrO4, (iv) Li, Cl(CH2)6OthP; MeOH, H, (v) H2, H,Pd/C, (vi) PBr3; KCN; KOH; HCI.
3.5-Dibenzyloxybenzoic acid (6) was esterified to give the ethyl ester (7) which was reduced to the alcohol (8), oxidation of which afforded 3,5dibenzyloxybenzaldehyde (9). Reaction with lithium and 6-chiorohexanol protected as the tetrahydropyranyl ether and then protective group removal gave the diol (10) (C J Baylis, S W D Odle and J H P Tyman, J.Chem.Soc.Perkin 1, Trans, 198 1,132, and unpublished work, 1974), which was hydrogenolysed to 7-(3,5-dihydroxyphenyl)heptanol. Conversion by known steps (A A Durrani, G C Sun and J H P Tyman., Lipids, 1982, 17, 561) to the bromide, 7-(3,5-dihydroxyphenyl)heptyl bromide, thence the nitrile and hydrolysis gave the acid (11), 8-(3,5- dihydroxyphenyloctanoic acid, identical to the product of mild oxidation of (2) In the proposed method, shown in Scheme 1, cardol (1) which contains 3 unsaturated constituents, the monoene (n =2, the diene (n = 4) and the triene (n = 6) is separated from technical cashew nut shell liquid.as described. The mixture is ozonised to give one product, 8-(3,5- dihydreoxyphenyl)octanal, after hydrogenation of the ozonide by the established method,, and this aldehyde is submitted to the Wittig reaction with the phosphonium salt of a 1 -bromoalkane having a carbon chain length C7, C9, Cli, C13. or Cl5 (R = 6, 8, 10, 12 or 14, to afford the 8(Z)-ailcene (3). This monoene is itself a minor constituent of the resorcinolic lipids in rye (Cereale secale). By reduction, chemically by diimide or by catalytic hydrogenation, the saturated product (4) is obtained which is a major constituent of cereal resorcinolic lipids.
By reaction of the aldehyde with the C7, phosphonium salt of(Z)-Br(CH2) 2CH=CHR, the C 15, 8(Z), 11(Z) diene would result, (5, R = C3H7). The C7 intermediate has been synthesised (M V Sargent and.Wangchareontrajkul, J. Chem. Soc. Perkin 1 Trans, 1989, 1171) Example 1 [Synthesis of 5-alkyiresorcinols from 8-(3,5- dihydroxyphenyl)octanal] Separation of Cardol (1, n = 0,2,4,6) In the separation of cardol from technical cashew nut shell liquid derived from Anacardium occidentale (J H P Tyman, I E Bruce and P Payne, Natural Products letters, 1492,1, 117-120), technical CNSL (58.lg) in light petroleum (500cm3) was treated with butane-1,4-diol (50cm3) and after separation of the two layers, the mixture gave upon aqueous dilution of the diol phase and solvent extraction, cardol (8.4g) containing some 2-methylcardol.
8-(3,5-dihydroxyphenyl)octanal (2) In the ozonolysis of unsaturated cardol, (M B Graham and J H P Tyman, J. Am. Oil Chemists' Soc. 2002, 79, 725-732, from unpublished work,1984), cardol (0.36g) in ethyl acetate (75cm3) at -78 C was treated with ozonised air and after TLC monitoring, the ozonide was catalytically hydrogenated with the addition of Pd/C (0. 25g). Alternatively, chemical reduction with zinc and acetic acid can be employed. Upon completion of reaction and work up by removal of volatile aldehydes, 8-(3,5-dihydroxyphenyl)octanal was obtained as a light brown oil. Mild reduction of the aldehyde with sodium borohydride gave the corresponding alcohol which was also obtained by lithium aluminium hydride reduction of(10).
5-[8(Z)-Pentadecenyllresorciuol, (3, R = C6H13). (15: 1)-cardol) It is proposed in this invention to synthesise this C 15 compound by the Wittig reaction of the preceding aldehyde with the triphenylphosphonium bromide salt of 7- bromoheptane prepared from triphenyiphosphine and 1-bromoheptane, or with a phosphonate (Horner-Emmons modification). By the use of 1 -bromononane, 1- bromoundecane, and I -bromotridecane phosphonium salts, in a similar way to the formation of this C15 alkene,.homologous C17, C19 and C21 alkenes respectively could be anticipated.
A precedent for this reaction exists in previous work carried out (J H P Tyman and S T Foo, unpublished work, 1974), In that study, the successful reaction of 8-(3- methoxyphenyl)octanal with triphenyiphosphonium heptyl bromide by the Wittig reaction in dimethylformamide solution containing sodium ethoxide, afforded a 65% yield of primarily the cis product, 5-[8(Z).-pentadecenyl] resorcinol dimethyl ether.
The required 8-(3-methoxyphenyl)octanal was synthesised from 8-(3methoxyphenyl)heptanol (J Caplin and J H P Tyman, J.Chem.Res., 1982(S), 34-35) by conversion to 8-(3-methoxyphenyl)heptylbromide, Grignard reaction with ethyl orthoformate and hydrolysis.
8-(3-methoxyphenyl)octanal (0.45g. 1.92x103mol) in dry DMF (1.2cm3) was added slowly to a suspension of triphenylphosphoniumheptyl bromide (1.65g, 3.65x103mol) and sodium ethoxide (0.22g, 3.20x103mol) in dry DMF (0. 60cm3) previouisly stirred for 30min.at OC and 30mm at 20C. The total mixture was reacted at 20 C for 22h.
then diluted with water, ethereally extracted, evaporated, extracted with light petroleum to remove triphenyl phosphine, and afforded the crude product (0.96g).
Preparative TLC purification with chloroform -light petroleum (40-60C). 3 0:70 gave the product spectroscopically identical with natural cis, (15:1) -cardanol metyl ether.
In the present proposed reaction of 8-(3,5-dihydroxyphenyl)octanal with phosphonium salts of 1-bromoheptane, lO-bromononane, 1-bromoundecane and 1- bromotridecane to produce (15:1), (17:1), (19:1) and (21:1)-cardols respectively, a two molar excess of the base sodium ethoxide would be required on account of the two aromatic hydroxyl groups.
Previous successful work on the synthesis of phenolic lipids in which phenolic intermediates were employed without protection of hydroxyl groups indicates that the present proposed application with dihydroxy resorcinolic intermediates has practical feasibilty and significance (i Caplin and J H P Tyman, .1. Chem. Res., 1982, (S), 34- 35; J H P. Tyman, C H. Khor and B G. Schofield, Chem. and Phys. of Lipids. 2002, 89, 101-108).
5-(Pentadecyl)resorcinol (4, R C6H13) It is proposed to synthesise this saturated compound in this invention by reduction of the previous alkene either by catalytic hydrogenation or by chemical reduction with hydrazine/air. A precedent for this reaction exists in previous work by the inventor as described in the following experiment.
Reduction of unsaturated cardol to saturated cardol (1, n =0) The chemical reduction process with hydrazine/air has been described for a number of related phenolic lipids (S K Lam and J H P Tyman, J. Chem. Soc.. Perkin Trans, 1982, 1942-1952; J H P Tyman and S J A Iddenten, J. Chem. Tech. and Biotech., 2005, in the press). Thus, unsaturated cardol (1.OOg) in ethanol (50cm3) containing hydrazine hydrate (2.OOg) at SOC was agitated and air passed through the mixture until monitoring by argentation TLC indicated complete reaction which required further additions of hydrazine, 2.OOg and 2.50g). recovery gave crystalline cardol (O.60g). Alternatively catalytic hydrogenation of the unsaturated compound in ethanolic solution with 5% palladium/carbon catalyst can be employed.
For the first ozonolysis step, cardol is a particularly valuable raw material because it is abundant (20%) in natural CNSL, 25% of which itself occurs in the raw cashew nut and 20% in technical CNSL derived from the natural product in the industrial decarboxylation process (J H P Tymari, Chemistry and Inndustry, London, 1980, 59).
Other naturally occurring phenolic lipids also contain cardol structural analogues although unlike cashew they are not abundant. They have been ozonised in experimental studies, for example to quote a few, Ginkgo biloba, (Chem, Pharm. Bull., 1987, 35, 3016 Grevillea pyramidalis, (Austral. J Chem., 1974, 27, 345), Pesoona ellipitica, (Austral. J. Chem., 1971, 24, 1925. Algal sources, Cystophora torulosa (Austral. J. Chem., 1977, 30, 2527) and other Anacardiacae such as Mangfera indica (.1 Agric. Food Chem., 1985, 33, 377), contain resorcinolic analogues although the % levels are considerably less and in some cases side chain unsaturation comprises double bonds at different and often at several positions so that mixtures of aldehyde products result, The use of cardol in the present invention represents as aspect of partial synthesis (J.H.P.Tyman, Partial and Semi-Synthesis with Biological Raw Materials, in Phytochemical Diversity, 195-209, Royal Soc. Chem., Cambridge, 1997
Claims (4)
1. The synthesis of 5-alkyiresorcinols with C 15, Cl 7, Cl 9, C2 I, C23 and C 25 side chains from 8-(3,5-dihydroxyphenyl)octanal, obtained by ozonolysis of cardol present in natural resorcinolic lipids such as Anacardium occidentale and its industrial decarboylation product, technicasi cashew nutshell liquid, (CNSL), by the use of chain extension and reductive reactions.
2. The synthesis of 8(Z)-monoenes with C15,C17, C19,C21,C23 and C25 sidechains by the use of the Wittig reaction or its modifications.
3. The synthesis of 8(Z),1 1(Z)-dienes with the same side chains by the use of the Wittig reaction or its modifications. (7
AMENDMENTS TO THE CLAIMS HAVE BEEN FILED AS FOLLOWS
1. A method of synthesis of 5-aikyiresorcinols with C15-C 25 side chains from 8- (3,5-dihydroxyphenyl)octanal, obtained by ozonolysis of cardol present in natural resorcinolic lipids such as Anacardiurn occidentale and its industrial decarboylation product, technical cashew nutshell liquid, (CNSL), by the use of Wittig, or its modifications, or other chain extension to give an 8(Z)monoene.
2. A method as claimed in Claimi comprising the reduction of die double bond in the side chain to yield the saturated analogues 3. A method as claimed in Claim 1 which comprises the step of dehydration of an 8hydroxy intermediate, obtained by (irignard chain extension, to yield a mixture of alkenes reducible to the corresponding saturated compounds.
4. A method as claimed in Claim 1 which comprises the step of reaction with a bromo (Z)-a]kene to yield the 8(Z), 11 (Z)-dienes.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB0517572A GB2429455B (en) | 2005-08-27 | 2005-08-27 | A method for the synthesis of 5-alkylresorcinols, (3,5-dihydroxy-n-alkylbenzenes) and 5-alk(en)ylresorcinols, from cardol via ozonolysis and chain extension |
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| Application Number | Priority Date | Filing Date | Title |
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| GB0517572A GB2429455B (en) | 2005-08-27 | 2005-08-27 | A method for the synthesis of 5-alkylresorcinols, (3,5-dihydroxy-n-alkylbenzenes) and 5-alk(en)ylresorcinols, from cardol via ozonolysis and chain extension |
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| GB0517572D0 GB0517572D0 (en) | 2005-10-05 |
| GB2429455A true GB2429455A (en) | 2007-02-28 |
| GB2429455B GB2429455B (en) | 2009-04-15 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2450682A (en) * | 2007-06-26 | 2009-01-07 | John Henry Paul Tyman | Use of benzyl protection in the synthesis of 5-n-alkylresorcinols |
| CN106562939A (en) * | 2015-10-08 | 2017-04-19 | 中国科学院微生物研究所 | Application of compound AJ-4 in preparation of medicine for treating or preventing influenza virus |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114903879B (en) * | 2022-06-23 | 2023-10-31 | 东北大学 | Use of 3-hydrocarbylphenol derivatives for the preparation of products for the prevention or treatment of hyperlipidaemia and related metabolic disorders |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001261693A (en) * | 2000-03-14 | 2001-09-26 | Natl Inst Of Advanced Industrial Science & Technology Meti | New o-glycoside type glycolipid and method for producing the same |
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2005
- 2005-08-27 GB GB0517572A patent/GB2429455B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001261693A (en) * | 2000-03-14 | 2001-09-26 | Natl Inst Of Advanced Industrial Science & Technology Meti | New o-glycoside type glycolipid and method for producing the same |
Non-Patent Citations (2)
| Title |
|---|
| Chemical & Pharmaceutical Bulletin, 1968, Vol. 16(11), pages 2282-2286 & Chemical Abstracts, abstr no 71:12716. * |
| Journal of the American Oil Chemists' Society, 2002, Vol. 79(7), pages 725-732 & Chemical Abstracts, abstr no 137:296531. * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2450682A (en) * | 2007-06-26 | 2009-01-07 | John Henry Paul Tyman | Use of benzyl protection in the synthesis of 5-n-alkylresorcinols |
| GB2450682B (en) * | 2007-06-26 | 2012-01-25 | John Henry Paul Tyman | Syntheses of 5-n-alkylresorcinols (5-n-alkyl-1,3-dihydroxybenzenes) from 8-(3,5-dibenzyloxyphenyl)octanal, obtained by ozonolysis from dibenzylcardol |
| CN106562939A (en) * | 2015-10-08 | 2017-04-19 | 中国科学院微生物研究所 | Application of compound AJ-4 in preparation of medicine for treating or preventing influenza virus |
| CN106562939B (en) * | 2015-10-08 | 2019-01-15 | 中国科学院微生物研究所 | Application of the compound AJ-4 in the drug that preparation treats or prevents influenza virus |
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| Publication number | Publication date |
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| GB2429455B (en) | 2009-04-15 |
| GB0517572D0 (en) | 2005-10-05 |
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