CN87100039A - Production method of carane aldehydic acid lactone - Google Patents
Production method of carane aldehydic acid lactone Download PDFInfo
- Publication number
- CN87100039A CN87100039A CN87100039.3A CN87100039A CN87100039A CN 87100039 A CN87100039 A CN 87100039A CN 87100039 A CN87100039 A CN 87100039A CN 87100039 A CN87100039 A CN 87100039A
- Authority
- CN
- China
- Prior art keywords
- carane
- acid lactone
- acid
- cis
- aldehydic acid
- 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.)
- Granted
Links
- 239000002253 acid Substances 0.000 title claims abstract description 16
- BWRHOYDPVJPXMF-UHFFFAOYSA-N carane Chemical compound C1C(C)CCC2C(C)(C)C12 BWRHOYDPVJPXMF-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 150000002596 lactones Chemical class 0.000 title claims abstract description 11
- 229930006741 carane Natural products 0.000 title claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 title 1
- XLOPRKKSAJMMEW-HTQZYQBOSA-N (-)-cis-chrysanthemic acid Chemical compound CC(C)=C[C@@H]1[C@H](C(O)=O)C1(C)C XLOPRKKSAJMMEW-HTQZYQBOSA-N 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 239000005892 Deltamethrin Substances 0.000 abstract description 2
- 229960002483 decamethrin Drugs 0.000 abstract description 2
- OWZREIFADZCYQD-NSHGMRRFSA-N deltamethrin Chemical compound CC1(C)[C@@H](C=C(Br)Br)[C@H]1C(=O)O[C@H](C#N)C1=CC=CC(OC=2C=CC=CC=2)=C1 OWZREIFADZCYQD-NSHGMRRFSA-N 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- -1 Carane aldehyde Chemical class 0.000 abstract 2
- 239000002917 insecticide Substances 0.000 abstract 1
- 239000002728 pyrethroid Substances 0.000 abstract 1
- BWRHOYDPVJPXMF-XHNCKOQMSA-N (1s,4s,6r)-4,7,7-trimethylbicyclo[4.1.0]heptane Chemical compound C1[C@@H](C)CC[C@@H]2C(C)(C)[C@H]12 BWRHOYDPVJPXMF-XHNCKOQMSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- XLOPRKKSAJMMEW-SFYZADRCSA-M (R,R)-chrysanthemate Chemical compound CC(C)=C[C@@H]1[C@@H](C([O-])=O)C1(C)C XLOPRKKSAJMMEW-SFYZADRCSA-M 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- XLOPRKKSAJMMEW-UHFFFAOYSA-N chrysanthemic acid Chemical compound CC(C)=CC1C(C(O)=O)C1(C)C XLOPRKKSAJMMEW-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 241001269238 Data Species 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Abstract
Carane aldehyde acid lactone, particularly 1R-carane aldehyde acid lactone, is a key intermediate for synthesizing high-efficiency pyrethroid insecticides, such as deltamethrin. The invention relates to a simple preparation method thereof: the carane aldehyde acid lactone with yield of more than 80% is prepared by ozonizing cis-chrysanthemic acid and reducing with zinc powder in an acid medium under a common cooling condition.
The method is simple and convenient, has high yield and good product purity, and the chiral center in the molecule does not change in the reaction process, so the method is particularly suitable for preparing the 1R-carane aldehyde acid lactone from the 1R-cis-chrysanthemic acid.
Description
The invention belongs to the pesticide intermediate class
Carane aldehydic acid lactone I
Particularly the 1R-isomer is the key intermediate of synthesizing efficient sterilant Deltamethrin.Document (1) journal is led suitable, anti-chrysanthemumic acid can prepare carane aldehydic acid lactone and trans carane aldehydic acid through ozonize, but report is not tested any details and reaction yield.Thereafter (USP3723469) reported the trans-chrysanthemate ozonize and can get trans carane aldehydic acid, though reactions steps is detailed, but reaction conditions is harsh (will be cooled to-80 ℃) very, aftertreatment is also very numerous and diverse, and has only 30～40% yield.
The objective of the invention is to find the short-cut method of a preparation carane aldehydic acid lactone.We find to carry out the chrysanthemumic acid ozonize under general refrigerative condition in acidic medium, and the yield (in chrysanthemumic acid) of carane aldehydic acid lactone can be up to more than 80%, and aftertreatment is very easy.
Implement 1
The 8.4g cis-chrysanthemic acid is dissolved in is in the highly acid 80ml ethyl acetate, then till-5～15 ℃ the liquor kalii iodide of feeding ozone in the scrubbing bottle that is associated in reactor exit becomes red-brown down.Feed then nitrogen about 15 minutes to drive the ozone that is dissolved in the reaction solution.Add 10ml water and 5g zinc powder reduction superoxide, suction filtration is to remove solid matter when no longer including superoxide in the question response liquid, with a small amount of solvent filter wash slag, tell the organic phase in the filtrate, washing, anhydrous magnesium sulfate drying, the decompression desolventizing, residue is placed promptly has crystal to separate out.Crystal 6 g is separated out in collection, and content 98.0% (high efficiency liquid chromatography analysis), yield are 84% (in cis-chrysanthemic acid) m.p.83.5～85 ℃.
NMR:
1H:(Cl
3CD; Interior mark: TMS; Ppm)
1.16(s，3H)，1.24(s，3H)；2.04(br.2H)；
5～7(br.2H)
13C；14.9；25.7(br)；30.8(br.)；37.2(br.)
96.8(br.)；174.7
The IR:(KBr compressing tablet)
3388；1725；1207；1187；1112cm
-1
It is identical that all physical datas and structure one cause the And literature value.
Implement 2
Condition and enforcement 1 are raw material with the 1R-cis-chrysanthemic acid just together.Get 7.8g 1R-carane aldehydic acid lactone from 11.2g 1R one cis-chrysanthemic acid.Purity is 101.1%, yield 84%, mp112～115 ℃ (α)
D 15=-104 ° (C=1%, ethanol)
Implement 3
Condition and enforcement 1 are raw material with the trans-chrysanthemate just together.Residue behind the desolventizing carries out underpressure distillation, can obtain the trans carane aldehydic acid of quite satisfied yield.
Reference (1) Konzo, Ueda; Et al.Agri.Biol.Chem.
34(7)
1119-1125(1970)
Claims (1)
1. one kind prepares carane aldehydic acid lactone method, it is characterized in that under general cooling conditions carrying out ozonize by cis-chrysanthemic acid in acidic medium, uses zinc powder reduction then.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87100039 CN1020192C (en) | 1987-01-06 | 1987-01-06 | Production method of carane aldehydic acid lactone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 87100039 CN1020192C (en) | 1987-01-06 | 1987-01-06 | Production method of carane aldehydic acid lactone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87100039A true CN87100039A (en) | 1988-07-20 |
| CN1020192C CN1020192C (en) | 1993-03-31 |
Family
ID=4812683
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 87100039 Expired - Fee Related CN1020192C (en) | 1987-01-06 | 1987-01-06 | Production method of carane aldehydic acid lactone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1020192C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1094125C (en) * | 1997-11-29 | 2002-11-13 | 中国科学院大连化学物理研究所 | Process for preparing high purity carane aldehyde |
| CN102391228A (en) * | 2011-12-26 | 2012-03-28 | 江苏扬农化工股份有限公司 | New synthetic method of Caronic anhydride |
| CN105267274A (en) * | 2015-11-12 | 2016-01-27 | 辽宁中医药大学 | Atractylenolide extract having antiparkinsonian effect, preparation method and application thereof |
-
1987
- 1987-01-06 CN CN 87100039 patent/CN1020192C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1094125C (en) * | 1997-11-29 | 2002-11-13 | 中国科学院大连化学物理研究所 | Process for preparing high purity carane aldehyde |
| CN102391228A (en) * | 2011-12-26 | 2012-03-28 | 江苏扬农化工股份有限公司 | New synthetic method of Caronic anhydride |
| CN105267274A (en) * | 2015-11-12 | 2016-01-27 | 辽宁中医药大学 | Atractylenolide extract having antiparkinsonian effect, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1020192C (en) | 1993-03-31 |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| C19 | Lapse of patent right due to non-payment of the annual fee |