CS261275B1 - Method of 2-methyl-7,8-octadecine preparation - Google Patents
Method of 2-methyl-7,8-octadecine preparation Download PDFInfo
- Publication number
- CS261275B1 CS261275B1 CS874380A CS438087A CS261275B1 CS 261275 B1 CS261275 B1 CS 261275B1 CS 874380 A CS874380 A CS 874380A CS 438087 A CS438087 A CS 438087A CS 261275 B1 CS261275 B1 CS 261275B1
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- CS
- Czechoslovakia
- Prior art keywords
- methyl
- preparation
- octadecin
- octadecine
- diglyme
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 title claims description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims abstract description 6
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 claims abstract description 4
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims abstract description 4
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 claims description 2
- 101150065749 Churc1 gene Proteins 0.000 claims description 2
- 102100038239 Protein Churchill Human genes 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000877 Sex Attractant Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 3
- HFOFYNMWYRXIBP-UHFFFAOYSA-N 2-decyl-3-(5-methylhexyl)oxirane Chemical compound CCCCCCCCCCC1OC1CCCCC(C)C HFOFYNMWYRXIBP-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- XAOFMTDKQYEOES-UHFFFAOYSA-N 1-bromo-5-methylhexane Chemical compound CC(C)CCCCBr XAOFMTDKQYEOES-UHFFFAOYSA-N 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- CJMUVMINGJFKIR-UHFFFAOYSA-N 2-(2-hydroxyethoxy)ethanol;methoxymethane Chemical compound COC.OCCOCCO CJMUVMINGJFKIR-UHFFFAOYSA-N 0.000 description 1
- PYLNKMIIIYYNRY-UHFFFAOYSA-N 2-[2-(2-hydroxyethoxy)ethoxy]ethanol;methoxymethane Chemical compound COC.OCCOCCOCCO PYLNKMIIIYYNRY-UHFFFAOYSA-N 0.000 description 1
- 241000408655 Dispar Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Způsob přípravy 2-metyl-7,8-oktadecinu vzorce I, (CH3)2CHCH2CH2CH2CH2C3CCH2CH2CH2CH2CH2- CH2CH2CH2CH2CH3 d>' který se připravuje tak, že na 1-bromdekan se působí l-lithio-7-metyl-l-oktinem v diglymu nebo v triglymu. 2-metyl-7,8- -oktadecin je klíčovým meziproduktem při syntéze disparluru pohlavního feromonu bekyně velkohlavé metodami acetylenové chemie.Process for preparing 2-methyl-7,8-octadecin formula I, (CH3) 2CHCH2CH2CH2CH2C3CCH2CH2CH2CH2CH2- CH2CH2CH2CH2CH3 d> ' which is prepared by 1-bromodecane is treated with 1-lithio-7-methyl-1-octine in diglyme or triglyme. 2-methyl-7,8- octocecin is a key intermediate in the synthesis of disparlur sex pheromone acetylenic methods chemistry.
Description
Předmět vynálezu se týká způsobu přípravy 2-metyl-7,8-oktadecinu.The present invention relates to a process for the preparation of 2-methyl-7,8-octadecin.
2-metyl-7,8-oktadecin je klíčovým meziproduktem při syntéze Disparluru - pohlavního feromonu bekyně velkohlavé (Portheria dispar L.) metodami acetylenové chemie (Shamshurin A. A., Rekhter M. A., Vlád L. A.: Khim. Prir. Soedin. 9 (4), 545 (1973); Eiter K.: Angew. Chem. 84 (2), 67 (1972)). Podle uvedené literatury je 2-metyl-7,8-oktadecin připravován reakcí 1-lithio-l-dodecinu s l-brom-5-metylhexanem. Nyní bylo zjištěno (Jonas. J., Slanina P., Humpa 0., Mazal C.: Chem. listy - připraveno k zaslání redakci), že 2-mety1-7,8-oktadecin lze připravit výhodněji jak co do výtěžku, tak co do jednoduchosti čištění.2-Methyl-7,8-octadecin is a key intermediate in the synthesis of Disparlur, the sex pheromone of the broad-headed rouse (Portheria dispar L.) by acetylene chemistry (Shamshurin AA, Rekhter MA, LA Government: Khim. Prir. Soedin. 9 (4), 545 (1973), Eiter K .: Angew Chem 84 (2), 67 (1972). According to the literature, 2-methyl-7,8-octadecin is prepared by reacting 1-lithio-1-dodecine with 1-bromo-5-methylhexane. It has now been found (Jonas. J., Slanina P., Humpa 0, Mazal C .: Chem. Sheets - ready to be sent to the editor) that 2-methyl-7,8-octadecin can be prepared more advantageously in both yield and yield. in terms of simplicity of cleaning.
Podle vynálezu byl nalezen způsob přípravy 2-mety1-7,8-oktadecinu vzorce I,According to the invention, a process for the preparation of 2-methyl-7,8-octadecin of formula I has been found,
CH.CH.
CH !^> CHCH2CH2CH2CH2C=CCH2CH2CH2CH2CH2CH2CH2CH2CH2CH3 který umožňuje zefektivnit syntézu disparluru jak co do výtěžku, tak co do náročnosti na čištění, sloučeninu vzorce I lze připravit reakcí l-lithio-7-metyl-l-oktinu s 1-bromdekanem v diglymu (dimetyletherdietylenglykolu) nebo v triglymu (dimetylhertrietylengylokolu).CH ! ^> CHCH 2 CH 2 CH 2 CH 2 C = CCH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 3 which makes the disparlure synthesis more efficient in terms of both yield and purity, the compound of formula I can be prepared by reacting 1-lithio-7-methyl-1-octin with 1-bromodecane in diglyme (dimethyl ether diethylene glycol) or in triglyme (dimethyl ether triethylene glycol).
Příklad 1Example 1
Roztok n-butyllithia v hexanu, připravený z 4,3 g lithia a 34,2 g 1-brombutanu ve 133 ml hexanu, byl pod atmosférou dusíku přidán k roztoku 24,3 g 7-metyl-l-oktinu v 300 ml diglymu, hexan byl oddestilován za normálního tlaku a roztok byl míchán 6 hodin při 120 až 130 °C. Poté bylo přidáno 44,3 g 1-bromdekanu v 50 ml diglymu, směs byla míchána a zahřívána na 120 až 140 °C 60 hodin a diglym byl oddestilován za sníženého tlaku. Destilační zbytek byl frakcionován za použití rotační vakuové odparky s vodní vývěvou a límcovou baňkou zařazenou mezi odparku a destilační baňku. Z olejové lázně tak bylo při 195 až 205 °C získáno 63 % 2-mety1-7,8-oktadecinu (sloučenina vzorce I), čistoty vyšší než 97 » (plynovou chromatografii na Carbowaxu 20 m při 200 °C), jehož 4h NMR, hmotnostní spektrum i chemické chování byly v plné shodě s údaji v uvedené literatuře.A solution of n-butyllithium in hexane, prepared from 4.3 g of lithium and 34.2 g of 1-bromobutane in 133 ml of hexane, was added under nitrogen to a solution of 24.3 g of 7-methyl-1-octine in 300 ml of diglyme, hexane was distilled off under normal pressure and the solution was stirred at 120-130 ° C for 6 hours. Then 44.3 g of 1-bromdecane in 50 ml of diglyme was added, the mixture was stirred and heated to 120-140 ° C for 60 hours and the diglyme was distilled off under reduced pressure. The distillation residue was fractionated using a rotary evaporator with a water pump and a flask flask placed between the evaporator and the distillation flask. From the oil bath and was at 195-205 ° C, yield 63% 2-mety1-7,8-oktadecinu (compound I), purity of greater than 97 »(by gas chromatography on a Carbowax 20 m at 200 ° C), the 4 h NMR, mass spectrum and chemical behavior were in full agreement with the data reported in the literature.
Příklad 2Example 2
Stejným postupem jako v příkladu 1 bylo ze ste jné; násady za použití stejného množství triglymu jako rozpouštědla připraveno 72 » 2-metyl-7,8-oktadecinu (sloučenina vzorce I) o čistotě vyšší než 97 % (stanoveno plynovou chromatografii).The same procedure as in Example 1 was the same; 72% 2-methyl-7,8-octadecin (compound of formula I) having a purity greater than 97% (determined by gas chromatography) was prepared using the same amount of triglyme as the solvent.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS874380A CS261275B1 (en) | 1987-06-15 | 1987-06-15 | Method of 2-methyl-7,8-octadecine preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS874380A CS261275B1 (en) | 1987-06-15 | 1987-06-15 | Method of 2-methyl-7,8-octadecine preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS438087A1 CS438087A1 (en) | 1988-06-15 |
| CS261275B1 true CS261275B1 (en) | 1989-01-12 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS874380A CS261275B1 (en) | 1987-06-15 | 1987-06-15 | Method of 2-methyl-7,8-octadecine preparation |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS261275B1 (en) |
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1987
- 1987-06-15 CS CS874380A patent/CS261275B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS438087A1 (en) | 1988-06-15 |
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