CN1020192C - Production method of carane aldehydic acid lactone - Google Patents
Production method of carane aldehydic acid lactone Download PDFInfo
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- CN1020192C CN1020192C CN 87100039 CN87100039A CN1020192C CN 1020192 C CN1020192 C CN 1020192C CN 87100039 CN87100039 CN 87100039 CN 87100039 A CN87100039 A CN 87100039A CN 1020192 C CN1020192 C CN 1020192C
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- Prior art keywords
- lactone
- carane
- acid
- carane aldehydic
- aldehydic acid
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Abstract
The present invention relates to a simple and convenient preparation method of carane aldehydic acid lactone, particularly to a simple and convenient preparation method of 1R-carane aldehydic acidic lactone as a key intermediate for synthesizing high-efficiency pyrethroid insecticide, such as deltamethrin, which comprises the steps that the carane aldehydic acid lactone with the yield more than 80% is prepared from cis-chrysanthemic acid by ozonization and znic powder reduction in acidic media under the general cooling condition. The method has the advantages of simplicity, convenience, high yield, good product purity and no change of chiral centers in molecules in the reaction process, and thus, is especially suitable for preparing the 1R-carane aldehydic acidic lactone from 1R-cis-chrysanthemic acid.
Description
The invention belongs to the pesticide intermediate class
Carane aldehydic acid lactone (I) [formal name used at school is a 3-formyl radical-2, the lactone of 2-dimethyl-cyclopropane-carboxylic acid]
Particularly the 1R-isomer is the key intermediate of synthesizing efficient sterilant Deltamethrin.Document [Konzo, Veda; Etal.Agri, Biol.Chem.34(7) 1119-1125(1970)] suitable, the anti-chrysanthemumic acid of report can prepare carane aldehydic acid lactone and trans carane aldehydic acid through ozonize, but report is not tested any details and reaction yield.Thereafter [US3723469] reported the trans-chrysanthemate ozonize and can get trans carane aldehydic acid, though reactions steps is detailed, reaction conditions is harsh (will be cooled to-80 ℃) very, and aftertreatment is also very numerous and diverse, and has only the yield of 30-40%.
The objective of the invention is to find the short-cut method of a preparation carane aldehydic acid lactone.We find in the strongly-acid medium to carry out the chrysanthemumic acid ozonize under-5-15 ℃ condition, 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, with a small amount of solvent filter wash slag when no longer including superoxide in the question response liquid, tell the organic phase in the filtrate, wet concentration, 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 is analyzed), yield is that 84%(is 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
All physical datas are consistent and identical with literature value with structure.
Implement 2
Condition and enforcement 1 are raw material with the 1R-cis-chrysanthemic acid just together.Get 7.8g1R-carane aldehydic acid lactone from the 11.2g1R-cis-chrysanthemic acid.Purity is 101.1%, yield 84%, m.p.112～115 ℃ [α]
15 D=-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, a kind of method for preparing carane aldehydic acid lactone is characterized in that under-5-15 ℃ 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 CN87100039A (en) | 1988-07-20 |
| CN1020192C true 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) |
Families Citing this family (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
Also Published As
| Publication number | Publication date |
|---|---|
| CN87100039A (en) | 1988-07-20 |
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