GB2085881A - A process for the preparation of 11-dodecen-1-ol and derivatives - Google Patents

A process for the preparation of 11-dodecen-1-ol and derivatives Download PDF

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GB2085881A
GB2085881A GB8132023A GB8132023A GB2085881A GB 2085881 A GB2085881 A GB 2085881A GB 8132023 A GB8132023 A GB 8132023A GB 8132023 A GB8132023 A GB 8132023A GB 2085881 A GB2085881 A GB 2085881A
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dodecen
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ester
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Egyt Gyogyszervegyeszeti Gyar
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/14Preparation of carboxylic acid esters from carboxylic acid halides
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/30Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/313Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00Preparation of carboxylic acid esters
    • C07C67/30Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

11-dodecen-1-ol and its acetic acid ester are prepared by reducing an alkyl dodec-12-enoate (V) and, optionally acetylating. The compounds (V) may be prepared from compounds of formula (IV> OCH-(CH2)9-COOR<1> (IV> by a method suitable for the formation of a vinyl group, and the compounds of formula (IV) may be prepared by the oxidation of an ester of the general formula (III> HO-CH2-(CH2)9-COOR<1> (III> wherein R<1> has the same meaning as above. Esters of formula (III) may be prepared in a variety of ways, such as the treatment of a corresponding haloester with a base, or the esterification of the corresponding acid. <IMAGE>

Description

SPECIFICATION A process for the preparation of 11-dodecen-1-ol and derivatives The process relates to a process for the preparation of 1 1-dodecen-l-oI and derivatives.
It is known that 1 1-dodecen-l-yl derivatives of the general formula (I), CH2=CH-(CH2)9-CH2-R (I) wherein R represents a hydroxyl group or an acetoxy group, can be found in the natural sex lure or sex pheromones of several insect species, and can be used to advantage in integrated plant protection. The compounds of general formula (I) have been extracted e.g. from the pheromones of the following pests: red bellworm (Diparopsis castanea) [B.F. Nesbitt, P.S. Beevor, R.A. Cole, R. Lester and R.G. Poppi: Nature, New Biol. 1973, 244(137)208; B.F. Nesbitt, F. Cole, R.A. Beevor, R. Lester and R.G. Poppi: J. Insect Physiol. 1975, 1907; R. J. Marks: Bull. Entomol.Res. 1976, 219; R. J. Marks: Bull. Entomol. Res. 1976, 427; R. J. Marks: Bull.
Entomol.Res. 1976, 243] and Eupoecilia ambiguella [P. Saglio, C. Descoins, M. Galloix, D. Jaouen and J.
Mercier: C. R. Reun. Pheromones Sex Lepid. 1976,119; P. Saglio, C. Descoins, M. Galiois, M. Lettere, D.
Jaouen and J. Mercier: Ann.Zool.Ecol.Anim. 1977, 5531. The compounds of the general formula (I) can serve as insect attractants for the above insects.
When used with other pheromone components, the compounds of the general formula (I) exert a stimulating effect on springworm (Spargonothis pilleriana): P. Saglio, E. Priesner, C. Descoins and M.
Gallois: C. R. Reun. Pheromones Sex.Lepid. 1976, 109; and show a pheromone-inhibiting effect on summer-fruittortrix (Adoxophyies orana): S. Voerman and A.K. Minks: Environm.Entom. 1973,751; S.
Voerman, A.K. Minks and N.W.H. Houx: Environmn.Entom. 1974, 701.
For the preparation of the derivative of the general formula (I), wherein R is an acexoty group, Bestmann et al. have elaborated a synthesis which was laid open with reference to their unpublished results [Chem.Phys.Lipids 24. 335(1979)]. The starting substance of their synthesis is the 11 -octadecenyl-1 -ol acetate, which is a scarcely available derivative of a natural substance. This compound is ozonolyzed into 11 -acetoxy-undecanol. Ozonolysis requires expensive equipment and can be applied only as a laboratory semi-micro method. The Wittig reaction of the 11 -acetoxy-undecanol with the corresponding alkylidenephoshorane results in the desired product with a low yield.
For the preparation of the compound of the general formula (I), in which R stands for a hydroxyl group, no synthetic method has been published in the technical literature.
According to the invention we provide a process for the preparation of the compounds of the general formula (I), in which R has the same meanings as defined above, which comprises reducing an ester of the general formula (V) CH2=CH-(Ch2)9-COOR7 (V) wherein R1 is a CiA alkyl group, followed, where a compound of formula (I) in which R represents an acetoxy group is desired, by acetylation of the compound of formula (I) in which R represents a hydroxyl group thus obtained.
The compound of general formula (V) may be prepared by a variety of methods. Such methods include the step of forming a compound of formula (V) from a compound of formula (IV) OCH-(CH2)9-COOR1 (IV) wherein R1 is as defined above, by a method enabling the formation of a vinyl group.
The compounds of general formula (IV) may be prepared by a variety of methods. Such methods include the step of oxidising a compound of formula (III) HO-CH2-(CH2)9-COOR1 (III) wherein R' is as defined above. Such oxidation may be achieved by methods known per se.
The ester of formula (ill) may be prepared by a variety of methods. Such methods include a1) reacting an 1 1-halogen-undecanic acid of the general formula (II), Hal-CH2-(CH2)9-COOH (II) wherein Hal represent a halogen atom, with a base, and reacting the 1 1-hydroxy-undecanic acid thus obtained with an aliphatic alcohol containing 1 to 4 carbon atom(s) preferably in the presence ofthe catalytic amount of an acid; or a2) reacting 1 1-hydroxy-undecanic acid with a CiA aliphatic alcohol preferably in the presence of the catalytic amount of an acid.
The halogen-undecanic acid of the general formula /II/ used as starting substance is a commercial product.
The conversion of the compounds of the general formula /II/ into the corresponding 11 -hydroxy-derivatives is carried out with the aid of an alkali or alkaline-earth hydroxide. Preferred representative of the alkali hydroxides is the sodium hydroxide. The reaction is preferably carried out in aqueous medium. One proceeds preferably under heating, particularly at the boiling points of the reaction mixture. As starting substance, preferably the 11 -bromoundecanic acid /II: Hal=Br/ is used. The 11 -hydroxy-undecanic acid thus-obtained can be isolated by acidifying the reaction mixture with a strong acid /e.g. hydrochloric, sulfuric acid, etc./ and filtering off the separated product.
The 1 1-hydroxy-undecanic acid thus-obtained is esterified into the ester of the general formula /II/. The reaction is preferably carried out with the aid of the corresponding alkanols. The excess of the alkanol can serve as reaction medium. The reaction is preferably carried out in the presence of the catalytic amount of an acid /e.g. hydrochloric, sulfuric, phosphoric, p-toluenesulfonic acid/. The reaction is performed under heating - preferably at the boiling point of the reaction mixture. The compounds of the general formula /III/ thus-obtained can be used for the next reaction steps after or without isolation.
The ester of the general formula /III/ is oxidized preferably with pyridinium-chlorochromate, pyridiniumbichromate or active manganese dioxide. As reaction medium aprotic soivents can be used. When oxidizing with pyridinium chlorochromate, the oxidation is preferably carried out in a halogenated aliphatic hydrocarbon /e.g. dichloromethane, chloroform, carbon tetrachlorid/. When oxidizing with manganese dioxide, aromatic hydrocarbons/e.g. benzene, toluene, xylene, etc./ are used as reaction medium. The reaction temperature varies between about 0 C and 60 "C. One proceeds preferably at room temperature.
The compound of the general formula /IV/ thus-obtained is converted into an ester of the general formula Nl. This reaction can be carried out with a method suitable to build a vinyl group. The compound of the general formula /lav/ is preferably treated with a mixture of methylene iodide, zinc and triethyl-aluminium. As reaction medium different ethers /e.g. diethyl ether, tetrahydrofurane, dioxane, etc./ can be used. The reaction temperature varies between 0 C and 60"C. One proceeds preferably at room temperature.
The compound of the general formula N/thus-obtained is reduced into 1 -dodecon-1 -ol /I; R=OH/. The reduction can be carried out with a complex metal hydride /e.g. lithium-aluminium hydride orsodium-bis-/ 2-methoxy-ethoxy/-aluminium-hydride/ in an ether-type solvent/e.g. diethyl ether, tetrahydrofurane, dioxane, etc./ or in an aromatic hydrocarbon /e.g. benzene, toluene, xylene/. It is also preferable to carry out the reaction with sodium in the presence of an alcohol. The reaction temperature varies between about 0 C and 60"C, one proceeds preferably at room temperature.
The 11 -dodecen-1 -ol thus-obtained is optionally converted into the 1 1-dodecen-1 -yl-acetate after or without isolation. The acetylation is carried out with acetic acid or a reactive derivative thereof. As acylating agent preferably acetyl chloride or acetic anhydride are used. When acetylating with acetyl chloride the reaction can be performed in an ethereous solvent/e.g. diethyl ether, dioxane, tetrahydrofurane/. When acetic an hydride is used as acyiating agent, the excess thereof can serve as reaction medium. The reaction is preferably carried out in the presence of an acid binding agent. For this purpose alkali carbonate /e.g. sodium or potassium carbonate/, alkali bicarbonates /e.g. sodium or potassium bicarbonate/ or organic bases /e.g.
pyridine, triethylamine, etc./ can be used. The reaction temperature varies between about 0 C and 80 "C, one proceeds preferably at about 20 C to 40 OC.
The advantage of the method according to the invention is that the desired compounds can be produced with a good yield also on industrial scale.
The process is illustrated by the following Examples of non-limiting character: EXAMPLE 1 Preparation of 1 1-hydroxy-undecanic acid/I, R=CH3COO-/ 13.2 g /0.05 moles/ of 1 1-bromoundecanic acid /II; Hal=Br/ are dissolved in 100 ml of 2N sodium hydroxide solution and the mixture is boiled for 5 hours. Then it is cooled and poured into 25 ml of concentrated hydrochloric acid, the separated crystalline product is filtered off and washed with water.
Yield: 9.1 g/90%/ M.p.: 69-70 C IR /KBr/: 3350, 1700cm1 1H-NMR /CDCl3/: 6.7 [s /wide/, 2H, OH]; 3.65 It, J=10 Hz, 2H, CH2-O/; 2.35 It, J=11 Hz, 2H, CH2-COO/; 1.1-1.9 /m, 16H, -CH2-/.
Analysis: C11H22O3/202.30/ calculated: C=65.31 % H=10.96 % found: C=65.10% H=11.10% EXAMPLE 2 Preparation ofmethyl- 1 1-hydroxy-undecanoate /III, R1 =CH3/ To a solution of 10.1 g /0.05 moles/ 11 11-hydroxy-undecanic acid in 50 mi of anhydrous methanol 0.3 ml of sulfuric acid are added, then the mixture is boiled for 6 hours. The hot solution is neutralized with 1.2 g of barium carbonate, cooled, filtered and the filtrate is evaporated in vacuo.
Yield: 9.7 g/90%/ IR /film/: 3400, 1735 cm 1 aH-NMR /CDCI3/: 3.70/s+t, 5H, COOCH3 + CH2O/; 2.33 /t, J=11 Hz, 2H, CH2-COO/; 1.1-1.9/m, 17H, -CH2- +OH/.
Analysis: C12H24O3/216.325/ calculated: C= 66.63% H=11.18% found: C= 66.42% H=11.06% EXAMPLE 3 Preparation of methyl- 10-formyl-decanoate /IV R1 = CH3/ 6.46 g /0.03 ml/ of pyridinium chlorochromate and 0.32 g /0.004 moles/of anhydrous sodium acetate are admixed with 50 ml of anhydrous dichloromethane, then a solution of 4.32 g /0.02 moles/ of methyl-11-hydroxy-undecanoate in 10 ml of anhydrous dichloromethane is added. The reaction mixture is stirred under inert gas/nitrogen or argon/at room temperature for 2.5 hours, then it is treated with 300 ml of anhydrous ether and the ethereous solution is decanted. This operation is repeated several times with a few anhydrous ether. The ethereous solutions are combined and filtered on Bentonitfilter, evaporated in vacuo, and the residue is distilled in vacuo.
Yield: 3.6 g /85 %/ B.p.: 111-113 C/0.3mm nD23=1,6695 IR/film/:2720, 1735 cm-1 1H-NMR /CDCI3/: 9.83 It, J=3Hz, 1 H, CHO/; 3.68/s, 3H, COOCH3/; 2.32/t, J=11Hz, 4H, CH2-COO+CH2-CHO/; 1.1-1.9/m 14H, -CH-/.
Analysis: C12H22O3/214.30/ calculated: C= 67.25% H=10.35% found: C= 67.10% H=10.28% EXAMPLE 4 Preparation of methyl-11-dodecenoate IV: R1 = CH3/ To a mixture of 8.39 g /0.03 moles, 2.93 ml/ of diiodomethane, 5.88 g /0.09 moles/of zinc dust and 50 ml of anhydrous tetrahydrofurane 0.69 g /0.006 moles, 0.83 ml/ of triethyl-aluminium are added under inert gas and under vigorous stirring, and stirring is continued for 20 minutes.Then the reaction mixture is cooled to room temperature, and a solution of 2.14 g/0.01 mole/of methyl-10-formyl-dodecanoate in 10 ml of anhydrous tetrahydrofurane are dropped under 15 to 20 minutes. The mixture is stirred at room temperature for an hour, then it is diluted with 100 ml of ether, water is added and the solution is acidified with 1 N hydrochloric acid.The aqueous phase is separated by decantation and extracted twice with a total amount of 60 ml of ether. The organic phases are combined and washed with 1 N hydrochloric acid, 5 % sodium hydrogen carbonate, 5 % sodium bisulfite, water and concentrated sodium chloride solution; dried over magnesium sulfate, the ether is removed and the residue is distilled in vacuo.
Yield: 1.85 g/87%/ B.p.: 110-112 C/0.3 mm nD23=1.4395 IR/film/: 1745, 1640 cm-1 H-NMR/CDCl3/: 5.5-6.3/n, 1H,/; 4.7-5.3/m, 2H, 12-H/; 3.65/s, 3H, COOCH3/; 2.32 It, J=11 Hz, 2H, CH2COO/; 2.2/t, J=15Hz, 2H, 10-H/; 1.1-1.9 /m, 14H, -CH2-/.
Analysis: C13H24O3/212.37/ calculated: C=73.54% H=11.39% found: C=73.58 % H=11.21 % EXAMPLE 5 Preparation of 1 1-dodecen-1-ol/l, R=OH/ To a suspension of 0.23 g /0.006 moles/of lithium-aluminium hydride in 20 ml of anhydrous ether a solution of 2.12 9 /0.01 moles/of methyl-1 1 -dodecenoate in 5 mi of anhydrous ether is added dropwise under inert gas, and the mixture is stirred at room temperature for an hour. Then it is decomposed with water under cooling, acidified with 1 N hydrochloric acid, and the upper ethereous phase is separated. The aqueous phase is shaken with ether, the ethereous phases are combined, washed with 1 N hydrochloric acid, water, concentrated sodium chloride solution and dried over magnesium sulfate.The ether is removed by distillation in vacuo and the residue is purified by column chromatography. /Kieselgel 60, benzene-acetone 10:2/ Yield: 1.6 g/88%/ Rf=0.28 /benzene-acetone 10:1/ IR/film/: 3350, 1640 cm-1 H-NMR/CDCl3/: 5.5-6.3/m, 1H, 11-H/; 4.7-5.3/m, 2H, 12-H/; 3.65 It, J=10 Hz, 2H, -CH2-O/; 2.10 Im, 2H, 10-H/; 1.1-1.9/m, 17H, -CHr +OH/.
Analysis: C12H240 184.33 calculated: C=78.19% H=13.12% found: C=78.06 % H=13.17% EXAMPLE 6 Preparation of 11-dodecen-1-yl-acetate/I, R=CH3COO/ To a solution of 1.84 g /0.01 mole/of 1 1-dodeccen-1-ol and 1.19 g /0.015 moles, 1.2 ml/ of anhydrous pyridine in 25 ml of anhydrous ether 0.86 g /0.011 moles, 0.71 ml/ of acetyl chloride are added and the mixture is stirred at room temperature for 10 hours. Then it is diluted with 50 ml of ether, washed with water, 1N hydrochloric acid, 5% sodium hydrogen carbonate, water again, concentrated sodium chloride and dried over magnesium sulfate. The solvent is removed and the residue is distilled in vacuo.
Yield: 1.7 g/75%/ B.p.: 96-98 C/0.3 mm nD23=1.4398 GC; Rt=20 min./SE 30; 3% Ch-AWSr 80-100; 150 C/ IR/film/: 1740, 1635, 120 cm-1 H-NMR/CDCl3/: 5.5-6.3/m, 1H, 11-H/; 4.7-5.3 /m, 2H, 12-H/; 4.18/t, J=10 Hz, 2H, CH2-O/; 2.05/s+m, 5H, COCH3+10-CH2/; 1.1-1.9/m, 16H, -CH2-/.
Analysis: C14H26O2/226.36 calculated: C=74.29% H=11.58% found: C=74.11% H=11.40 %

Claims (1)

1. A process for the preparation of 1 -dodecen-1 -ol and derivatives of the general formula (I) CHP=CH - (CH2)9- CH2- R (I) wherein R represents a hydroxyl group or an acetoxy group which comprises reducing an 1 1-dodecen-1-yl ester of the general formula (V) CH2=CH-(CH2)9-COOR1 (V) wherein R1 is a CiA alkyl group, and, where a compound of formula (I) in which R represents an acetoxy group is desired, acetylating the 11-dodecen-1-ol thus obtained.
2. A process as claimed in claim 1 wherein the compound of formula (V) as defined in claim 1 is prepared by the reaction of a compound of formula (IV) OCH-(CH2)s-COOR1 (IV) wherein R1 is as defined in claim 1 with a compound enabling the formation of a vinyl group.
3. A process as claimed in claim 2 wherein the compound of formula (IV) as defined in claim 2 is prepared by the oxidation of a compound of formula (III) HOCH2-(CH2)9-COOR1 (Ill) wherein R1 is as defined in claim 1.
4. A process as claimed in claim 3 wherein the compound of formula (III) as defined in claim 3 is prepared by reacting a 11 -halogen-undecanic acid of the general formula (II), HaI-CH2(CH2)-COOH (II) wherein hal represents a halogen atom with an alkali metal or alkaline-earth metal hydroxide.
5. A process as claimed in claim 3 wherein the compound of formula (III) as defined in claim 3 is prepared by the reaction of 1 1-hydroxy-undecanic acid with an aliphatic alcohol in the presence of a catalytic amount of sulfuric, hydrochloric phosphoric, or p-toluenesulfonic acid.
6. A process as claimed in any of claims 3 to 5 wherein the oxidation of the 11 -hydroxy-undecanic ester of the general formula (III), wherein R1 has the same meaning as defined in claim 1, is carried out using pyridinium chlorochromate, pyridinium bichromate or active manganese dioxide.
7. A process as claimed in any of claims 2 to 6 wherein the 11 -hydroxy-undecanic formly ester of formula (IV) is converted into the 1 1-dodecen-1-yI ester of the general formula (V) using a mixture of methylene iodide, zinc and triethyl-aluminium.
8. A process as claimed in any of claims 1 to 7 wherein the 11 -dodecen-1 -yl ester of the general formula (V) is reduced with complex metal hydride, or with sodium metal in the presence of an alcohol.
9. A process as claimed in claim 1 wherein acetyiation is carried out with acetic acid or a reactive derivative thereof.
10. A process as claimed in claim 1 substantially as hereinbefore described.
11. A process as claimed in claim 1 substantially as hereinbefore described with reference to the accompanying Examples.
New claims or amendments to claims filed on 4th Feb 1982 Superseded claims 1,2 New or amended claims:
1. A process for the preparation of 11 -dodecen-1 -ol and derivatives of the general formula (I) CH2=CH-(CH2)9-CH2-R (I) wherein R represents a hydroxyl group oran acetoxy group which comprises reacting a compound of formula (IV) OCH-(CH2)9-COOR (II) wherein R1 is a CiA alkyl group, with a compound enabling the formation of a vinyl group, followed by reduction of the 11-dodecen-1-yl esterformed of the general formula (V) CH2=CH-(CH2)s-COOR1 (V) wherein R1 is as defined above, and, where a compound of formula (I) in which R represents an acetoxy group is desired, acetylating the 11-dodecen-1-ol thus obtained.
GB8132023A 1980-10-24 1981-10-23 A process for the preparation of 11-dodecen-1-ol and derivatives Withdrawn GB2085881A (en)

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HU80802575A HU180386B (en) 1980-10-24 1980-10-24 Process for producing 11-dodecen-1-ol and 11-dodecen-1-yl-acetate of insect-feromone activity

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4560792A (en) * 1982-07-20 1985-12-24 Phillips Petroleum Company Disproportionation of functional olefins
EP0341538A1 (en) * 1988-05-04 1989-11-15 BASF Aktiengesellschaft 1-Tert.-butoxy-omega-alkenes and their use in aroma compositions
WO2017087710A2 (en) 2015-11-18 2017-05-26 Provivi, Inc. Production of fatty olefin derivatives via olefin metathesis
US9695385B2 (en) 2013-03-13 2017-07-04 Stepan Company Surfactants based on monounsaturated fatty alcohol derivatives
US11155505B2 (en) 2017-02-17 2021-10-26 Provivi, Inc. Synthesis of pheromones and related materials via olefin metathesis

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1096345B (en) * 1959-02-28 1961-01-05 Bayer Ag Process for the preparation of hexadecadiene- (10, 12) -ol- (1)
CA961862A (en) * 1971-04-23 1975-01-28 Andre Comeau Trans-8-trans-10-dodecadien-1-o1

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4560792A (en) * 1982-07-20 1985-12-24 Phillips Petroleum Company Disproportionation of functional olefins
EP0341538A1 (en) * 1988-05-04 1989-11-15 BASF Aktiengesellschaft 1-Tert.-butoxy-omega-alkenes and their use in aroma compositions
US10287530B2 (en) 2013-03-13 2019-05-14 Stepan Company Surfactants based on monounsaturated fatty alcohol derivatives
US11560530B2 (en) 2013-03-13 2023-01-24 Stepan Company Surfactants based on monounsaturated fatty alcohol derivatives
US9695385B2 (en) 2013-03-13 2017-07-04 Stepan Company Surfactants based on monounsaturated fatty alcohol derivatives
US20200261898A1 (en) * 2015-11-18 2020-08-20 Provivi, Inc. Production of fatty olefin derivatives via olefin metathesis
EP3377465A4 (en) * 2015-11-18 2019-10-09 Provivi, Inc. Production of fatty olefin derivatives via olefin metathesis
US10596562B2 (en) 2015-11-18 2020-03-24 Provivi, Inc. Production of fatty olefin derivatives via olefin metathesis
CN108473390A (en) * 2015-11-18 2018-08-31 普罗维维公司 Fatty alkene derivatives are produced by olefin metathesis
US11077433B2 (en) * 2015-11-18 2021-08-03 Provivi, Inc. Production of fatty olefin derivatives via olefin metathesis
IL259459B (en) * 2015-11-18 2022-07-01 Provivi Inc Production of fatty olefin derivatives via olefin metathesis
CN108473390B (en) * 2015-11-18 2022-08-09 普罗维维公司 Production of aliphatic olefin derivatives by olefin metathesis
WO2017087710A2 (en) 2015-11-18 2017-05-26 Provivi, Inc. Production of fatty olefin derivatives via olefin metathesis
US11779911B2 (en) 2015-11-18 2023-10-10 Provivi, Inc. Production of fatty olefin derivatives via olefin metathesis
EP4234522A3 (en) * 2015-11-18 2023-10-25 Provivi, Inc. Production of fatty olefin derivatives via olefin metathesis
US11155505B2 (en) 2017-02-17 2021-10-26 Provivi, Inc. Synthesis of pheromones and related materials via olefin metathesis

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PT73870B (en) 1983-01-25
YU252981A (en) 1983-10-31
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BE890748A (en) 1982-04-16
IT8124627A0 (en) 1981-10-22
RO82277A (en) 1983-09-26
GR74694B (en) 1984-07-04
ES506524A0 (en) 1982-08-16
HU180386B (en) 1983-02-28

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