GB2139220A - Preparation of /E/3,7- dimethyl-2-7-octadien-1-yl propanoate - Google Patents
Preparation of /E/3,7- dimethyl-2-7-octadien-1-yl propanoate Download PDFInfo
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- GB2139220A GB2139220A GB08406933A GB8406933A GB2139220A GB 2139220 A GB2139220 A GB 2139220A GB 08406933 A GB08406933 A GB 08406933A GB 8406933 A GB8406933 A GB 8406933A GB 2139220 A GB2139220 A GB 2139220A
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- octadien
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical compound CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 title claims abstract description 7
- 238000002360 preparation method Methods 0.000 title claims description 13
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000002798 polar solvent Substances 0.000 claims abstract description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims abstract description 13
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 claims abstract description 13
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000002378 acidificating effect Effects 0.000 claims abstract description 11
- 239000003463 adsorbent Substances 0.000 claims abstract description 11
- -1 halo compound Chemical class 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052987 metal hydride Inorganic materials 0.000 claims abstract description 8
- 150000004681 metal hydrides Chemical class 0.000 claims abstract description 8
- 125000002252 acyl group Chemical group 0.000 claims abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 3
- 150000002367 halogens Chemical class 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- 229930008411 3,7-dimethylocta-2,6-dien-1-ol Natural products 0.000 claims description 10
- GLZPCOQZEFWAFX-UHFFFAOYSA-N KU0063794 Natural products CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000012280 lithium aluminium hydride Substances 0.000 claims description 6
- GUGRBFQNXVKOGR-UHFFFAOYSA-N butyl hypochlorite Chemical compound CCCCOCl GUGRBFQNXVKOGR-UHFFFAOYSA-N 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 abstract description 10
- IXZDIALLLMRYOU-UHFFFAOYSA-N tert-butyl hypochlorite Chemical compound CC(C)(C)OCl IXZDIALLLMRYOU-UHFFFAOYSA-N 0.000 abstract description 6
- 241000586568 Diaspidiotus perniciosus Species 0.000 abstract description 4
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 26
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 18
- HWJHWSBFPPPIPD-UHFFFAOYSA-N ethoxyethane;propan-2-one Chemical compound CC(C)=O.CCOCC HWJHWSBFPPPIPD-UHFFFAOYSA-N 0.000 description 12
- 239000003208 petroleum Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 9
- 235000019341 magnesium sulphate Nutrition 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 241000607479 Yersinia pestis Species 0.000 description 4
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 235000010265 sodium sulphite Nutrition 0.000 description 3
- BYDRTKVGBRTTIT-UHFFFAOYSA-N 2-methylprop-2-en-1-ol Chemical compound CC(=C)CO BYDRTKVGBRTTIT-UHFFFAOYSA-N 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N diisobutylaluminium hydride Substances CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000004936 stimulating effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- NDQXKKFRNOPRDW-UHFFFAOYSA-N 1,1,1-triethoxyethane Chemical compound CCOC(C)(OCC)OCC NDQXKKFRNOPRDW-UHFFFAOYSA-N 0.000 description 1
- RIFSGUJLMACJMI-UHFFFAOYSA-N 3,7-dimethylocta-2,7-dien-1-ol Chemical compound CC(=C)CCCC(C)=CCO RIFSGUJLMACJMI-UHFFFAOYSA-N 0.000 description 1
- LOFHPLKGPULNQP-UHFFFAOYSA-N 4-methylpent-4-en-1-ol Chemical compound CC(=C)CCCO LOFHPLKGPULNQP-UHFFFAOYSA-N 0.000 description 1
- 238000005821 Claisen rearrangement reaction Methods 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 206010061217 Infestation Diseases 0.000 description 1
- 235000014443 Pyrus communis Nutrition 0.000 description 1
- 239000000877 Sex Attractant Substances 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000004166 bioassay Methods 0.000 description 1
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 238000003965 capillary gas chromatography Methods 0.000 description 1
- 125000006355 carbonyl methylene group Chemical group [H]C([H])([*:2])C([*:1])=O 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- HIGQPQRQIQDZMP-UHFFFAOYSA-N geranil acetate Natural products CC(C)=CCCC(C)=CCOC(C)=O HIGQPQRQIQDZMP-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 150000002905 orthoesters Chemical class 0.000 description 1
- 239000003016 pheromone Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
- C07C33/02—Acyclic alcohols with carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/58—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of halogen, e.g. by hydrogenolysis, splitting-off
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/287—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/297—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A compound of the formula <IMAGE> is prepared by a./ reacting /E/-3,7-dimethyl -2,6-octadien-1-ol of the formula /II/ <IMAGE> with a propionating agent, preferably propanoic chloride, reacting the propanoate thus obtained with a tert.butyl hypohalide, preferably tert.butyl hypochlorite in a moderately acidic adsorbent, preferably Kieselgel, reacting the halo compound of the general formula /III/ thus obtained <IMAGE> wherein R stands for propionyl and Hal represents halogen, with a moderately reactive metal hydride in a polar solvent; or b./ reacting /E/-3,7-dimethyl-2,6-octadien-1-ol of the formula /II/ with a tert.butyl hypohalide, preferably hypochlorite in a moderately polar solvent, in the presence of a moderately acidic adsorbent, preferably Kieselgel, treating the halo compound ofthe general formula /III/, wherein R represents hydrogen and Hal is as defined above, with a reducing agent, reacting the alcohol of the formula /IV/ thus obtained <IMAGE> with a propionating agent, preferably propanoic chloride; or c./ converting/E/-3,7-dimethyl-2,6-octadien-1-ol of the formula /II/ with an acylating agent, preferably acetic anhydride, into a compound of the general formula /V/, <IMAGE> wherein R<1> is a C1-5 acyl group, adding a tert.butyl hypohalide, preferably tert.butyl hypochlorite, to the C7 double bond thereof in an aprotic, moderately polar solvent, in the presence of a moderately acidic adsorbent, preferably Kieselgel, reducing the compound of the general formula /III/ thus obtained, wherein R is a C1-5 acyl group, with a metal hydride, reacting the alcohol of the formula /IV/ thus obtained with a propionating agent, preferably propanoic chloride; and separating the compound of the formula /I/ thus obtained from the reaction mixture. Traps for destroying male San Jose Scale are baited with the compounds of formula I.
Description
SPECIFICATION
Process for the preparation of /E/ - 3,7 - dimethyl - 2,7 - octadien -1 - yl propanoate
The invention relates to a new process for the preparation of/El- 3,7 - dimethyl - 2,7 - octadien -1 -yl propanoate.
It is known that the/El- 3,7 - dimethyl - 2,7 - octadien -1 - yl propanoateof;theformula/I/
produces a significantly strong stimulating reaction on male San Jose scale/Qudraspidiotus perniciosus,
Comstock/.
The San Jose scale is a serious worldwide pest that attacks all parts of host trees including the fruit. Its widespread and serious infestations particularly of fruit trees/such as apple and pear/ make it a pest of economic importance. Its breeding is very rapid, and owing to the short reproduction time/three generations every year/the new infections become quickly widespread.
Roelofs et al. [M. K. Gieselman, R. E. Rice, R. A.
Jones and W. L. Roelofs: J. Chem, Ecol., 5,891/1979/] demonstrated that the sex pheromone of this pest consisted of a 2:3 mixture of/ZI- 3,7 - dimethyl - 2,7 octadien -1 -yl propanoate and 7 - methyl -3 methylene-7-octen-1 -yi propanoate. Greenhouse bioassay and field tests have shown that eitherthe two compounds independently or the mixture thereof produce a strong stimulating reaction on male San
Jose scale. Consequently these derivatives can be applied to combatthis pest, to indicate the beginning of swarming orto obtain information on the appearancethereof.
Anderson and Hen rick showed that the stereoisomer of the pheromone component, the /E/-3,7dimethyl - 2,7 - octadien - 1 - yl propanoate is superior in activitythan the natural sex lure, so can be appliedto advantage in plant protection/USA Patent
Specification No. 4,223,012/.
The compound oftheformula/I/has been synthe- tized by Henrick et al. 2 - Methyl - 2 - propen - 1 - ol was used as starting substance. The reaction of 2 - methyl - 2 - propen - 1 - ol with triethyl orthoacetate in the presence of propanoic acid gave via the orthoester
Claisen rearrangement ethyl 4 - methyl - 4 - pentanoate, which was reduced with lithium aluminium hydride. The 4 - methyl - 4 - penten - 1 - ol thus obtained was reacted with the dibromo compound of triphenylphosphine, the 5 - bromo - 2 - methyl - 1 pentenethus obtained was converted with lithium metal intothe corresponding lithium compound, which was reacted with cuprous iodide in the presence oftetramethylethylenediamine to give di /4 - methyl -4- penten - 1 -yl/cuprous iodide.The reaction of the latter compound with methyl -/2 butynoatel in ether gave methyl - [lEl - 3,7 - dimethyl 2,7 - octadienoate], which was reduced with diisobutylaluminium hydride to obtain/El- 3,7 - dimethyl 2,7 - octadien - 1 - ol. Finally, esterification with propanoic anhydride in the presence of pyridine gave the compound ofthe formula/IA The above synthesis is uneconomical because of the high number of the cumbersome reaction steps and the expensive reactants/triphenyl phosphine, lithium metal, diisobutylaluminium hydridel.
The aim of the present invention was to provide a more economical process forthe preparation of the compound ofthe formula/Il, which can be more readily carried out also on an industrial scale.
According to the invention the/El- 3,7 - dimethyl 2,7 - octadien - 1 - yl propanoate of the formula/I/can be prepared by a new and simple process consisting of fewer reaction steps than the known synthesis, characterized by a./ reacting/El- 3,7- dimethyl - 2,6 - octadien - 1 - ol of the formula /II/
with a propionating agent, preferably with propanoic chloride, reacting the propanoate thus obtained with avert. butyl hypohalide in a moderately polar solvent, in the presence of a moderately acidic adsorbent, preferably Kieselgel, reacting the halo compound of the general formula /III/ thus obtained
wherein Rstandsforpropionyl and Hal represents halogen, with a moderately reactive metal hydride in a polar solvent; or b./ reacting/El- 3,7 - dimethyl - 2,6 - octadien - 1 - ol with a tert. butyl hypohalide, preferably tert. butyl hypochlorite in a moderately polar solvent, in the presence of a moderately acidic adsorbent, preferably Kieselgel, treating the halo compound of the general formula /III/, wherein R represents hydrogen and Hal is as defined above, with a reducing agent, reacting the alcohol of the formula /IV/thus obtained
with a propionating agent, preferably propanoic chloride; or c.lconverting lEl- 3,7 - dimethyl - 2,6 - octadien 1 - ol ofthe formula Ill/with an acylating agent, preferably acetic anhydride, into a compound of the general formula Nl,
wherein
R is a C1-5 acyl group,
adding a tert. butyl hypohalide, preferably tert. butyl
hypochlorite, to the C6 double bond thereof in an
aprotic, moderately polar solvent, in the presence of a
moderately acidic adsorbent, preferably Kieselgel, reducing the compound of the general formula II Ill thus obtained, wherein R is a C1-5 acyl group and Hal is as defined above, with a metal hydride, reacting the alcohol of the formula /IV/thus obtained with a propionating agent, preferably propanoic chloride, and separating the compound ofthe formula Il/thus obtained from the reaction mixture.
The /E/-3,7-dimethyl-2,6-octadien-1-ol of the formula/II/used as starting substance is a cheap commercial productorcan be obtained easilyfrom natural sources.
According to variant a./ of the process according to the invention/El- 3,7 - dimethyl - 2,6 - octadien -1 - ol is converted into the corresponding propanoate, which is then reacted with a tert. butyl hypohalide.
This latter reaction is carried out in a moderately polar solvent. Forthis purpose hexane or the homologous compoundsthereof/e.g. pentane, heptane/can be used. The halo compound obtained in the reaction is converted into the aimed compound of the formula/I/ preferably with sodium borohydride in a polar solvent. As solvent alcohols, dimethylformamide or dimethyl sulfoxide can be used.
According to variant b./ of the process according to the invention/El- 3,7 - dimethyl - 2,6 - octadien - 1 - ol is reacted with a tert. butyl hypohalide, preferably hypochlorite, in the presence of a moderately acidic adsorbent, in a moderately polar solvent. For this purpose preferably hexane or the homologous compounds thereof can be used. The halo compound of the general formula/Ill/thus obtained is isolated from the reaction mixture and treated with a reducing agent, preferably with lithium aluminium hydride.
The alcohol of the formula IIVI is separated from the reaction mixture and converted into the compound of the formula Il/with a propionating agent, preferably propanoic chloride.
According to variant c.Iofthe process according to the invention/El- 3,7 - dimethyl - 2,6 - octadien -1 - ol is reacted with an acylating agent, preferably acetic anhydride. The compound oftheformulaIVlthus obtained isthen treated with a tert. butyl hypohalide, preferably hypochlorite in an aprotic, moderately polar solvent. Forthis purpose hexane or the homologous compounds thereof can be used. The reaction is performed in the presence of a moderately acidic adsorbent.The compound ofthegeneral formula /III/thus obtained is then reduced with a metal hydride, preferably lithium aluminium hydride
Into the alcohol of the formula/IV/.The latter compound is then separated from the reaction mixture and converted into the aimed compound of the formula Il/with propionating agent, preferably propanoic chloride.
The invention is illustrated by the following Exam ples of non-limTing character.
Example 1 a./Preparation of/E/-3,7-dimethyl-2,6-ocatdien-1 ylpropanoate [N/:R=CO-CH2-CH3]
30.8 g /35 ml, 0.2 moles/of/El- 3,7 - dimethyl - 2,6
octadien - 1 - ol and 23.1 g /32 ml, 0.23 moles/of
triethylamine are dissolved in 100 ml of anhydrous
ether, and 20.4 g /19 ml, 0.22 molesl of propanoic
chloride are dropped to the solution within one hour,
under mixing and cooling /0 C/. The reaction mixture
is stirred for further one hour at 0 C, poured onto
crushed ice, the upper ether phase is separated, washed with water and saturated sodium chloride solution and dried over magnesium sulfate.The
solution is filtered, the solvent is distilled off and.the residue is distilled in vacuo.
Yield: 39.0 g/86%/
B.p.: 76-78 C/0.3 mm, 40 Pa
Gc:tR=5.40/capillary column, 15 m x 0.2 mm, stationary phase SE 54, t=99 , Packard capillary gas chromatography/
TLC: Rf = 0.55/petroleum ether-acetone 5:0.1/
IR/film/: 1735/CO/, 1660/C=C/, 1460, 1380, 1360, l270,ll70,1080,1040, 1010,940,890 cm1.
H-NMR/CDCl3/:1.0/3H, t, J=7 Hz, CH3/, 1.2-2.2 /13H, m, 3CH3m 2CH2/, 2.3/2H, q, J=7 Hz, COCH2/, 4.45 /2H, d, J=7 Hz, CH2-O/, 4.95/1H, m, C6 C=CHI, 5.25 /1 H,t,J=6 Hz, C2 C=CH/.
MS: M+210/ < 1/, 136/251,121/30/, 107/91,93/55/, 81/13, 80/17, 69/100/, 57/63/, 41/75/.
b./ Preparation of/E/- 6-chloro -3,7-dimethyl-2,7- octadien-1-yl propanate [III]:R=CO-CH2-CH3,
Hal=Cl]
A suspension of 30.0 g /0.142 moles/of/E/- 3,7 dimethyl - 2,6 - octadien - 1 -yl propanoate and 35 g of
Kieselgel 60 in 400 ml of anhydrous hexane is cooled to OOC, and 18.5 g/19.3 ml, 0.170 mole/oftert. butyl hypochlorite are dropped under vigorous stirring within 5 minutes.The mixture is stirred first 0 C for half an hourthen at room temperature for one hour. It is filtered, the filtrate is washed successively with 10 % sodium sulfite solution and 50 ml of water and dried over the magnesium sulfate.The solvent is distilled off in vacuo and the residue is purified by column chromatographylKieselgel 60, petroleum ether-acetone 5:0.1/.
Yield: 28.5 g /82 %I.
TLC: Rf=0.36 Ipetroleum ether-acetone 5:0.1/.
IR/film/: 1735/CO/, 1670, 1645/C=C/, 1460, 1380, 1360, 1270, 1170, 1085, 1010, 960, 905, 805 cm-1.
H-NMR/CCl4/: # 1.1/3H, t, J=7 Hz, CH3/, 1.8/6H, br.s. 2 CH3/, 1.8-2.55/6H, m, 3CH2/, 4.3/2H, m, CH2-Ol, 4.85/3H, m, CH2=C and CH-Cl/, 5.25/1H, m, CH=C/.
Ms: M+ 244/ < 1/, 172/7/, 170/20/, 135/54/, 121/27/, 119/56/, 107/28/, 93/71/, 91/44/, 81/100/, 79/52/, 74 /72/, 68/67/, 57/81/, 38/24/, 36/77/.
c./ Preparation of/E/-3,7-dimethyl-2,7- octadien - 1ylpropanoate
6.1 g /0.164 moles/ of sodium borohydride and 123 g/0.098 moles/of lithium iodide are dissolved in 100 ml of anhydrous dimethylformamide, and a solution of 20.0 g /0.082 moles/of/El- 6 - chloro - 3,7 - dimethyl - 2,7 - octadien - 1 -yl propanoate in 10 ml of anhydrous dimethylformamide is dropped within 45 minutes. The reaction mixture is stirred at 60 C for 3 hours, cooled, diluted with 500 ml of ether and poured onto a 5% cold hydrogen chloride solution.
The organic phase is separated, the aqueous phase is extracted three times with a total amount of 20 ml of ether, the ether solutions are combined, washed successively with saturated sodium hydrogen carbonate solution and water and dried over magnesium sulfate. The solvent is distilled off and the residue is distilled in vacuo. The main fraction/b.p.: 76-85 C/0.3 mm, 40 Pa/ is purified by column chromatography IKieselgel 60, petroleum ether-acetone 5:0.1/.
Yield: 6.5g/37.7 %/
TLC: Rf = 0.65/benzene/ GC: tR = 5.25/capillarycolumn,15 15mx0.2mm, stationary phase, SE 54, t = 99 , Packard capillary gas chromatograph/.
IR/film/: 1730/CO/,1660, 1640/C=C/,1450, 1380, 1355, 1260, 1200, 1160, 1075, 1000, 940, 890 cm-1.
H-NMR/CDCl3/: # 1.15/3H, t, J=7 Hzm CH3/, 1.7/6H, m, 2CH3/, 1.7-2.3/6H, m, 3CH2/2.45/2H, q, J=7 Hz,
CH2/, 4.6/2H, d, J=7 Hz, CH2-O/, 4.65/2H, m, CH2=C/, 5.35/1 H, m, C=CH/.
Ms:M+210/ < 1/, 136/19/, 121/31/, 107/15, 93/58/, 81/29/, 80/19/, 69/58/, 57/70/, 41/100/.
Example 2 a./Preparation of/E/-6-chloro-3,7-dimethyl-2,7octadien-1-of[/III/:R=H, Hal=Cl]
A suspension of 3.4 g /3.9 ml, 0.022 moles/of/E/- 3,7 - dimethyl - 2,6 - octadien - 1 - ol and 9.0 g of
Kieselgel in 60 ml ofanhydroushexaneiscooledto 0 C and 2.9g/3 ml, 0.026 moles/of tert.butyl hypochlorite are added within 5 minutes. The reaction mixture is stirred for half an hour, filtered, the filtrate is diluted with 100 ml of ether and poured onto 50 ml of 10 % cold sodium sulfite solution. The upper ethereal phase is separated, washed with water, dried over magnesium sulfate, the solvent is distilled off in vacuo and the residue is purified by column chromatography/Kieselgel 60, petroleum ether-acetone 5:1.5/.
Yield: 2.65 g/63 %/
TLC: Rf=0.38/petroleum ether-acetone 5:1/
IR/film/: 3300/OH/, 1670, 1645/C=C/, 1460, 1380, 1100, 1000, 905 cm-1.
H-NMR/CDCl3/# 1.7/3H, s, C3-CH3/, 1.8/3H, s,
C7-CH3/, 2.05/4H, mo, 2CH2/, 4.15/2H, d, J=7 Hz, CH2-O/, 4.7/1 H, m, CH-Cl/, 4.95/2H, d, J=7 Hz,
CH2=C/, 5.4/1 H, m, CH=C/.
Ms:M+ 188/4/, 152/8/, 135/13/, 134/14/, 109/31/, 95 /30/, 71/94/, 68/100/, 41/81/.
b./ Prepararion of/E/-3,7- dimethyl - 2,7 - octadien - 1 -ol/IVI To a suspension of 1.85 g/0.048 moles/of lithium aluminium hydride in 50 ml of anhydroustetrahydrofuran a solution of 6.0 g/0.032 moles/of 6 - chloro - 3,7 -dimethyl -2IE/,7 -octadien-1-of in 10 ml of an hydrous tetrahydrofu ran is added within half an hour, and the mixture is refluxed for 3 hours under stirring. Then ethyl acetate and water are added, the mixture is extracted three times with a total amount of 200 ml of ether, the ethereal phases are combined, washed with saturated sodium hydrogen carbonate solution and water and dried over magnesium sulfate.The solvent is distilled off in vacuo and the residue is purified by column chromatography IKieselgel 60, petroleum ether-acetone 5:0.1/.
Yield: 3.04g/62%/.
TLC: Rf=0.47/petroleum ether-acetone 5:1/.
IR/film/: 3300/OH/,1670, 1650/C=C/,1460, 1380, 1100, 1005, 895 cm-1 1H-NMR/CDCl: 6 1.65-2 /12H, m, 2 CH3, 3CH2/, 4.05/2H, d, J=7 Hz/, 4.6/2H, br.s., CH2=C/, 5.35/1 H, m,
CH=C/.
Ms:M+ 154/4/, 136/16/. 123/16/, 121/20/, 109/17/, 107/131,96/371,83/36/, 81/411,71/401,69/100/, 55/47/, 41/94/.
c./ Preparation of/E/- 3,7-dimethyl- 2,7-octadien -1yl propanate /I/
A solution of 2.4g/0.015 molesl of 3,7 - dimethyl 2,7 - octadien - 1 - ol and 1.73 9/2.4 ml,0.017 moles/of triethylamine in 20 ml of anhydrous ether is cooled to 0 C, and 1.56 g/1.5 ml, 0.017 moles/ of propanoic chloride are dropped within half an hour. The reaction mixture is stirred for one hour, then poured onto ice water, extracted with ether, the ethereal solution is washed successively with water and saturated sodium chloride solution and dried over magnesium sulfate. The solvent is distilled off and the residue is purified by column chromatography IKieselgel 60, petroleum ether-acetone 5:0.1/.
Yield: 1.87 9 /57 %/, the product is identical to the compound prepared according to Example 1.
Example 3 ad Preparation of/E/- 3.7 - dimethyl - 2,6 - octadien - 1 yl-acetate [NI: R=COCH3]
10.0 g/11.4 ml, 0.065 moles/of/E/-3,7-dimethyl2,6-octadien-1-ol and 7.2 g/10 ml, 0.07 moles/of triethylamine are dissolved in 50 ml of an hydrous ether, and 5.9 g/0.075 moles/of acetic chloride are dropped at 0 C under stirring and cooling, within one hour. The reaction mixture is stirred forfurther one hour at 0 C, poured onto crushed ice, the upper ether phase is separated, the ethereal solution is washed successively with water and saturated sodium chloride solution and dried over magnesium sulfate. The solvent is distilled off and the residue is distilled in vacuo.
Yield: 11.85g/93%/.
B.p.: 64-680C/0.3 mm, 40 Pa
TLC:Rf=0.72/benzene/
IR/film/: 1730/CO/. 1650/C=CI, 1460, 1380, 1360, 1260, 1150, 1060, 940, 890 cm-1.
b./ Preparation of/E/-6-chloro - 3,7- dimethyl - 2,7 - octadien - 1 - ylacetate [/III/: R=COCH3, Hal=CI] A suspension of 11.8 9 /0.06 moles/of/E/- 3,7 dimethyl - 2,6 - octadien - 1 - yl acetate and 25 9 of
Kieselgel 60 in 300 ml of ahydrous hexane is cooled to 0 C and 8.1 g/8.7 ml, 0.074 moles/ of tert. butyl hypochlorite are added dropwise within 5 minutes, under stirring. The mixture is stirred at 0 C for half an hour, then filtered, the filtrate is washed successively with 10 % sodium sulfite solution and water and dried over magnesium sulfate. The solvent is distilled off in vacuo and the residue is purified by column chroma tog raphy/Kieselgel 60, petroleum ether-acetone 5:0.1/.
Yield: 10.6 g/76 %/
TLC: Rf=0.44/petroleum ether-acetone 5:0.1/
IR/film/: 1730/CO/,1660, 1640/C=C/,1460, 1380, 1260, 1150, 1080, 945, 900 cm-1.
c./Preparation of/E/-3,7-dimethyl-2,7- octadien - 1 - ol /IV/
To a suspension of 2.46 9/0.062 moles/ of lithium
aluminium hydride in 50 ml ofanhydroustetrahydro- furan a solution of 4.87 g /0.021 moles/of/El- 6 - chloro -3,7 - dimethyl -2,7-octadien - 1 -yl acetate in
10 ml ofanhydroustetrahydrofuraneareadded within half an hour, and the mixture is refluxed for 2
hours, under stirring. Then the reaction is quenched with ethyl acetate and water, the mixture is extracted three times with total amount of 300 ml of ether, the ether solutions are combined, washed successively with saturated sodium hydrogen carbonate solution and water and dried over magnesium sulfate. The solvent is distilled off and the residue is purified by column chromatography IKieselgel 60, petroleum ether-acetone 5:0.1/.
Yield: 1.68 g /52 %/, the product is identical to the compound prepared according to Example 2/b, which can be converted into the aimed compound of the formula Il/according to Example 2/c.
Claims (6)
1. A process for the preparation of/E/-3,7- dimethyl - 2,7 - octadien - 1 - yl propanoate of the formula 111.
characterized by a./reacting/E/-3,7-dimethyl-2,6-octadien-1-ol of the formula /II/
with a propionating agent, perferably propanoic chloride, reacting the propanoate thus obtained with atert. butyl hypohalide, preferablytert. butyl hypochlorite in a moderately polar solvent, in the presence of a moderately acidic adsorbent, preferably Kieselgel, reacting the halo compound of the general formula /III/thus obtained,
wherein Rstandsforpropionyl and Hal represents halogen, with a moderately reactive metal hydride in a polar solvent; or reacting lEl- 3,7 - dimethyl - 2,6 - octadien - 1 -ol of the formula II II with a tert. butyl hypohalide, preferably hypochlorite, in a moderately polar solvent, in the presence of a moderately acidic adsorbent, preferably Kieselgel, treating the halo compound of the general formula /III/, wherein R represents hydrogen and Hal is as defined above, with a reducing agent, reacting the alcohol of the formula /IV/
with a propionating agent preferably propanoic chloride; or c./converting lEl- 3,7 - dimethyl - 2,6 - octadien - 1 -ol oftheformula/ll/with an acylating agent, preferably aceticanhydride, into a compound ofthe general formula no
wherein R' is a C1.5 acyl group, adding atert. butyl hypohalide, preferablytert. butyl hypochlorite, to the C6 double bond thereof in an aprotic, moderately polar solvent, in the presence of a moderately acidic adsorbent preferably Kieselgel, reducing the compound of the general formula /111/ thus obtained, wherein R is a C1-5 acyl group, with a metal hydride, reacting the alcohol oftheformula/lV/ thus obtained with a propionating agent, preferably propanoic chloride; and separating the compound of theformula /I/thus obtained from the reactiion mixture.
2. A process according to variant a./ of claim 1, characterized by reacting /E/ - 3,7 - dimethyl - 2,6 octadien - 1 -yl propanoate with a tert. butyl hypohalide in hexane or in a homologous compound thereof.
3. A process accordingto varianta./of claim 1, characterized by using as moderately reactive metal hydride sodium borohydride.
4. A process as claimed in variant b./or c./of claim 1, characterized by reducing the halo compound of the formula /111/ into the alcohol of the formula with lithium aluminium hydride.
5. A process substantially as hereinbeforedescribed in any one of Examples 1 to3.
6. Acompoundofthegeneralformula lwhen produced by a process as claimed in any one of claims 1 to 5.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HU83911A HU189247B (en) | 1983-03-18 | 1983-03-18 | Process for producing 3,7-dimethyl-2/e/-oktadien-1-yl-propionate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8406933D0 GB8406933D0 (en) | 1984-04-18 |
| GB2139220A true GB2139220A (en) | 1984-11-07 |
Family
ID=10952015
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08406933A Withdrawn GB2139220A (en) | 1983-03-18 | 1984-03-16 | Preparation of /E/3,7- dimethyl-2-7-octadien-1-yl propanoate |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JPS59196842A (en) |
| AU (1) | AU2582684A (en) |
| FR (1) | FR2542734A1 (en) |
| GB (1) | GB2139220A (en) |
| HU (1) | HU189247B (en) |
| IT (1) | IT1196052B (en) |
| PT (1) | PT78265B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0873982A1 (en) * | 1997-04-25 | 1998-10-28 | Kuraray Co., Ltd. | Process for preparing polyprenols |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4223012A (en) * | 1979-04-02 | 1980-09-16 | Zoecon Corporation | Method for control of San Jose scale |
-
1983
- 1983-03-18 HU HU83911A patent/HU189247B/en not_active IP Right Cessation
-
1984
- 1984-03-16 JP JP59049372A patent/JPS59196842A/en active Pending
- 1984-03-16 IT IT20077/84A patent/IT1196052B/en active
- 1984-03-16 PT PT78265A patent/PT78265B/en unknown
- 1984-03-16 AU AU25826/84A patent/AU2582684A/en not_active Abandoned
- 1984-03-16 FR FR8404097A patent/FR2542734A1/en active Pending
- 1984-03-16 GB GB08406933A patent/GB2139220A/en not_active Withdrawn
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0873982A1 (en) * | 1997-04-25 | 1998-10-28 | Kuraray Co., Ltd. | Process for preparing polyprenols |
| US5981811A (en) * | 1997-04-25 | 1999-11-09 | Kuraray Co., Ltd. | Process for preparing polyprenols |
Also Published As
| Publication number | Publication date |
|---|---|
| PT78265A (en) | 1984-04-01 |
| JPS59196842A (en) | 1984-11-08 |
| IT8420077A0 (en) | 1984-03-16 |
| IT1196052B (en) | 1988-11-10 |
| FR2542734A1 (en) | 1984-09-21 |
| AU2582684A (en) | 1984-09-20 |
| PT78265B (en) | 1986-04-30 |
| HUT33949A (en) | 1985-01-28 |
| GB8406933D0 (en) | 1984-04-18 |
| HU189247B (en) | 1986-06-30 |
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