CA1165770A - Process for stereoselectively synthetizing cyclopropane carboxylates as intermediates for pyrethroids - Google Patents
Process for stereoselectively synthetizing cyclopropane carboxylates as intermediates for pyrethroidsInfo
- Publication number
- CA1165770A CA1165770A CA000380843A CA380843A CA1165770A CA 1165770 A CA1165770 A CA 1165770A CA 000380843 A CA000380843 A CA 000380843A CA 380843 A CA380843 A CA 380843A CA 1165770 A CA1165770 A CA 1165770A
- Authority
- CA
- Canada
- Prior art keywords
- compound
- process according
- dehydrohalogenation
- solvent
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims abstract description 31
- VEMKTZHHVJILDY-UXHICEINSA-N bioresmethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OCC1=COC(CC=2C=CC=CC=2)=C1 VEMKTZHHVJILDY-UXHICEINSA-N 0.000 title description 9
- 239000000543 intermediate Substances 0.000 title description 8
- YMGUBTXCNDTFJI-UHFFFAOYSA-N cyclopropanecarboxylic acid Chemical class OC(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-N 0.000 title description 6
- 230000003407 synthetizing effect Effects 0.000 title 1
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 13
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims description 61
- 238000006243 chemical reaction Methods 0.000 claims description 36
- 239000002904 solvent Substances 0.000 claims description 30
- 238000006704 dehydrohalogenation reaction Methods 0.000 claims description 28
- 239000012454 non-polar solvent Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 22
- 229940126062 Compound A Drugs 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 18
- 238000010992 reflux Methods 0.000 claims description 15
- 230000000707 stereoselective effect Effects 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 12
- -1 alicyclic secondary amine Chemical class 0.000 claims description 11
- 150000003335 secondary amines Chemical class 0.000 claims description 11
- 150000004678 hydrides Chemical class 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 229910052794 bromium Chemical group 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 150000003141 primary amines Chemical class 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 6
- 239000002585 base Substances 0.000 description 27
- IHZNYURVTWMJCI-UHFFFAOYSA-N ethyl 6-bromo-6,7,7,7-tetrafluoro-3,3-dimethylhept-4-enoate Chemical compound CCOC(=O)CC(C)(C)C=CC(F)(Br)C(F)(F)F IHZNYURVTWMJCI-UHFFFAOYSA-N 0.000 description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 13
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 10
- 239000011541 reaction mixture Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 239000012074 organic phase Substances 0.000 description 8
- 235000019441 ethanol Nutrition 0.000 description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 150000002170 ethers Chemical class 0.000 description 5
- QQGCJLQAXNKFTR-UHFFFAOYSA-N ethyl 4,6-dibromo-6,7,7,7-tetrafluoro-3,3-dimethylheptanoate Chemical compound CCOC(=O)CC(C)(C)C(Br)CC(F)(Br)C(F)(F)F QQGCJLQAXNKFTR-UHFFFAOYSA-N 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000002798 polar solvent Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229950011148 cyclopropane Drugs 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229910000104 sodium hydride Inorganic materials 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 3
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 3
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 2
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical group C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004703 alkoxides Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 239000002917 insecticide Substances 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- BFNMOMYTTGHNGJ-UHFFFAOYSA-N 2,2-dimethylcyclopropane-1-carboxylic acid Chemical class CC1(C)CC1C(O)=O BFNMOMYTTGHNGJ-UHFFFAOYSA-N 0.000 description 1
- PTQGFDXPHNRDCV-UHFFFAOYSA-N 3-formyl-2,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1(C)C(C=O)C1C(O)=O PTQGFDXPHNRDCV-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 101150002414 GLC3 gene Proteins 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- YMGUBTXCNDTFJI-UHFFFAOYSA-M cyclopropanecarboxylate Chemical compound [O-]C(=O)C1CC1 YMGUBTXCNDTFJI-UHFFFAOYSA-M 0.000 description 1
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical compound C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- USPVNSDVCUTNJN-UHFFFAOYSA-N ethenyl cyclopropanecarboxylate Chemical compound C=COC(=O)C1CC1 USPVNSDVCUTNJN-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- MNWFXJYAOYHMED-UHFFFAOYSA-N heptanoic acid Chemical compound CCCCCCC(O)=O MNWFXJYAOYHMED-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 239000002728 pyrethroid Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- IOVGROKTTNBUGK-SJCJKPOMSA-N ritodrine Chemical compound N([C@@H](C)[C@H](O)C=1C=CC(O)=CC=1)CCC1=CC=C(O)C=C1 IOVGROKTTNBUGK-SJCJKPOMSA-N 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT23180A/80 | 1980-07-02 | ||
| IT8023180A IT1131883B (it) | 1980-07-02 | 1980-07-02 | Processo per la sintesi stereoselettiva di ciclopropancarbossilati intermaedi per piretroidi |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1165770A true CA1165770A (en) | 1984-04-17 |
Family
ID=11204601
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000380843A Expired CA1165770A (en) | 1980-07-02 | 1981-06-29 | Process for stereoselectively synthetizing cyclopropane carboxylates as intermediates for pyrethroids |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4442301A (en19) |
| EP (1) | EP0043143B1 (en19) |
| JP (1) | JPS5745141A (en19) |
| CA (1) | CA1165770A (en19) |
| DE (1) | DE3171009D1 (en19) |
| IT (1) | IT1131883B (en19) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2499979A1 (fr) * | 1981-02-13 | 1982-08-20 | Roussel Uclaf | Procede d'epimerisation d'acides trans chrysanthemiques |
| US4772695A (en) * | 1982-09-24 | 1988-09-20 | Societe Nationale Des Poudres Et Explosifs | Process for the preparation of vinyl carbamates |
| JPH0773422B2 (ja) * | 1983-06-22 | 1995-08-02 | 山本電気株式会社 | 偏平用モーター電機子の製造装置 |
| GB9311054D0 (en) * | 1993-05-28 | 1993-07-14 | Zeneca Ltd | Preparation of cyclopropane esters |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5340741A (en) * | 1975-06-24 | 1978-04-13 | Sumitomo Chem Co Ltd | Novel preparation of 2,2-dimethyl-3-b,b-dihalovinyl-cyclopropanecarboxylic acid ester |
| JPS5912103B2 (ja) * | 1975-12-26 | 1984-03-21 | ザイダンホウジン サガミチユウオウカガクケンキユウシヨ | カルボンサンエステルノセイゾウホウホウ |
| US4330675A (en) * | 1977-01-24 | 1982-05-18 | Imperial Chemical Industries Limited | Halogenated esters |
| GB2000764B (en) * | 1977-03-23 | 1982-04-28 | Ici Ltd | Halogenated esters |
| IN150399B (en19) * | 1978-01-20 | 1982-09-25 | Fmc Corp | |
| US4243677A (en) * | 1978-01-20 | 1981-01-06 | Fmc Corporation | Insecticidal perhaloalkylvinylcyclopropanecarboxylates |
| BG48921A3 (en) * | 1978-02-28 | 1991-06-14 | Montedison Spa | Method for destroying of insects |
| US4258202A (en) * | 1978-02-28 | 1981-03-24 | Montedison S.P.A. | Cyclopropanecarboxylic acids and esters |
| DE2831193A1 (de) * | 1978-07-15 | 1980-01-24 | Bayer Ag | Fluoralkenylsubstituierte cyclopropancarbonsaeureester und ihre verwendung als insektizide |
-
1980
- 1980-07-02 IT IT8023180A patent/IT1131883B/it active
-
1981
- 1981-06-26 JP JP56098502A patent/JPS5745141A/ja active Granted
- 1981-06-29 US US06/278,676 patent/US4442301A/en not_active Expired - Fee Related
- 1981-06-29 CA CA000380843A patent/CA1165770A/en not_active Expired
- 1981-07-02 EP EP81105152A patent/EP0043143B1/en not_active Expired
- 1981-07-02 DE DE8181105152T patent/DE3171009D1/de not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5745141A (en) | 1982-03-13 |
| EP0043143A3 (en) | 1982-10-13 |
| US4442301A (en) | 1984-04-10 |
| DE3171009D1 (en) | 1985-07-25 |
| IT1131883B (it) | 1986-06-25 |
| EP0043143A2 (en) | 1982-01-06 |
| JPH0148255B2 (en19) | 1989-10-18 |
| EP0043143B1 (en) | 1985-06-19 |
| IT8023180A0 (it) | 1980-07-02 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |