MD4247C1 - Synthesis process of cis-8-dodecenyl acetate - sex pheromone of plum fruit moth Grapholitha funebrana Tr. - Google Patents
Synthesis process of cis-8-dodecenyl acetate - sex pheromone of plum fruit moth Grapholitha funebrana Tr.Info
- Publication number
- MD4247C1 MD4247C1 MDA20120126A MD20120126A MD4247C1 MD 4247 C1 MD4247 C1 MD 4247C1 MD A20120126 A MDA20120126 A MD A20120126A MD 20120126 A MD20120126 A MD 20120126A MD 4247 C1 MD4247 C1 MD 4247C1
- Authority
- MD
- Moldova
- Prior art keywords
- cis
- alcohol
- synthesis
- sex pheromone
- dodecenyl acetate
- Prior art date
Links
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 26
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 26
- SUCYDSJQVVGOIW-WAYWQWQTSA-N 8Z-Dodecenyl acetate Chemical compound CCC\C=C/CCCCCCCOC(C)=O SUCYDSJQVVGOIW-WAYWQWQTSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 8
- 230000008569 process Effects 0.000 title claims abstract description 7
- 239000000877 Sex Attractant Substances 0.000 title abstract description 9
- 241000923682 Grapholita funebrana Species 0.000 title abstract 3
- 241000659076 Grapholitha Species 0.000 title description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 45
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 10
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 10
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 7
- BUDQDWGNQVEFAC-UHFFFAOYSA-N Dihydropyran Chemical compound C1COC=CC1 BUDQDWGNQVEFAC-UHFFFAOYSA-N 0.000 claims abstract description 5
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012346 acetyl chloride Substances 0.000 claims abstract description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 4
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 238000010511 deprotection reaction Methods 0.000 claims abstract description 3
- 125000003186 propargylic group Chemical group 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 230000003993 interaction Effects 0.000 claims 2
- 150000001408 amides Chemical class 0.000 claims 1
- 230000009466 transformation Effects 0.000 claims 1
- -1 acetylene alcohol Chemical compound 0.000 abstract description 5
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 abstract description 5
- 230000004071 biological effect Effects 0.000 abstract description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 abstract description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 235000021018 plums Nutrition 0.000 abstract description 2
- 125000001412 tetrahydropyranyl group Chemical group 0.000 abstract description 2
- 230000021736 acetylation Effects 0.000 abstract 1
- 238000006640 acetylation reaction Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 26
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000004215 Carbon black (E152) Substances 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- 239000003016 pheromone Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YEQONIQGGSENJQ-PLNGDYQASA-N (z)-dodec-8-en-1-ol Chemical compound CCC\C=C/CCCCCCCO YEQONIQGGSENJQ-PLNGDYQASA-N 0.000 description 2
- PDKMGJGWXQNQGL-UHFFFAOYSA-N 1-chloro-1-iodohexane Chemical compound CCCCCC(Cl)I PDKMGJGWXQNQGL-UHFFFAOYSA-N 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000001568 sexual effect Effects 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000004809 thin layer chromatography Methods 0.000 description 2
- VBYPENUQSSBEKQ-UHFFFAOYSA-N 1-bromohexane hydrobromide Chemical compound Br.BrCCCCCC VBYPENUQSSBEKQ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000659001 Grapholitha molesta Species 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000000397 acetylating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007333 cyanation reaction Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001030 gas--liquid chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 231100000925 very toxic Toxicity 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Invenţia se referă la sinteza compuşilor organici nesaturaţi, în special la sinteza feromonului sexual al viermelui prunelor, care se utilizează în protecţia prunului. The invention relates to the synthesis of unsaturated organic compounds, in particular to the synthesis of the sexual pheromone of the plum worm, which is used in the protection of the plum.
Este cunoscută schema de sinteză a cis-8-dodecenilacetatului [1], care constă în alchilarea derivatei de Li a pentinei-1 cu clor-iodhexanul (1) cu prelungirea catenei carbonice până la C12 cu ajutorul reacţiei de cianare. The synthesis scheme of cis-8-dodecenyl acetate [1] is known, which consists in the alkylation of the Li derivative of pentine-1 with chloro-iodohexane (1) with the extension of the carbon chain up to C12 with the help of the cyanation reaction.
Dezavantajul acestei scheme de sinteză este că ea include hidrocarbura acetilenică pentin-1, care este o substanţă foarte toxică şi costisitoare şi clor-iodhexanul, care se obţine în câteva stadii. Calea de sinteză a alcoolului-cheie acetilenic (5) este complicată şi include multe stadii. The disadvantage of this synthesis scheme is that it includes the pentyne-1 acetylenic hydrocarbon, which is a very toxic and expensive substance, and chloroiodohexane, which is obtained in several stages. The synthesis pathway of the key acetylenic alcohol (5) is complicated and includes many stages.
De asemenea este cunoscută schema de sinteză a cis-8-dodecenilacetatului [2], care constă în condensarea reagentului Grigniard al bromurii 1-brom-5-(1-etoxi)etoxipentan (care se obţine în câteva stadii) cu 1-bromhept-3-in - obţinut prin reacţia de oxietilare a hidrocarburii acetilenice pentin-1 cu esterul 2-cloretilvinil. Această schemă de sinteză, de asemenea, include hidrocarbura acetilenică pentin-1 (neajunsurile căreia au fost menţionate mai sus), iar sinteza alcoolului-cheie - dodecin-8-ol-1, în general, este complicată şi include multe stadii. The synthesis scheme of cis-8-dodecenyl acetate [2] is also known, which consists in the condensation of the Grignard reagent of 1-bromo-5-(1-ethoxy)ethoxypentane bromide (which is obtained in several stages) with 1-bromohept- 3-in - obtained by the oxyethylation reaction of pentyne-1 acetylenic hydrocarbon with 2-chloroethylvinyl ester. This synthesis scheme also includes the acetylene hydrocarbon pentyn-1 (the shortcomings of which were mentioned above), and the synthesis of the key alcohol - dodecin-8-ol-1, in general, is complicated and includes many stages.
Problema pe care o rezolvă invenţia propusă este excluderea din sinteza cis-8-dodecenilacetatului a hidrocarburii acetilenice pentin-1 şi a dihalogenilor ori a halogenacetalilor şi simplificarea schemei de sinteză a cis-8-dodecenilacetatului. The problem that the proposed invention solves is the exclusion from the synthesis of cis-8-dodecenyl acetate of the pentyn-1 acetylenic hydrocarbon and dihalogens or haloacetals and the simplification of the synthesis scheme of cis-8-dodecenyl acetate.
Noutatea invenţiei constă în aceea că legătura triplă în procedeul de obţinere a cis-8-dodecenilacetatului se introduce prin utilizarea alcoolului propargilic (care este de zeci de ori mai ieftin ca hidrocarbura pentin-1), şi anume: se obţine alchilderivata alcoolului propargilic cu legătura triplă în poziţia 2 - în acest caz nonin-2-ol-1 (1, schema de sinteză), care, mai apoi, în prezenţa amidurii de sodiu şi etilendiamină se transformă în alcoolul acetilenic nonin-8-ol-1 (2) cu legătura triplă (acetilenică) terminală, adică are loc regruparea legăturii triple în alchilderivatele alcoolului propargilic, care se utilizează cu succes în sinteza cis-8-dodecenilacetatului - feromonul sexual al viermelui prunelor. The novelty of the invention consists in the fact that the triple bond in the process of obtaining cis-8-dodecenyl acetate is introduced by using propargylic alcohol (which is tens of times cheaper than pentyne-1 hydrocarbon), namely: the alkyl derivative of propargylic alcohol with the bond triple in position 2 - in this case nonin-2-ol-1 (1, synthesis scheme), which, later, in the presence of sodium amide and ethylenediamine, transforms into the acetylenic alcohol nonin-8-ol-1 (2) with the terminal triple (acetylenic) bond, that is, the regrouping of the triple bond takes place in the alkyl derivatives of propargylic alcohol, which is successfully used in the synthesis of cis-8-dodecenyl acetate - the sex pheromone of the plum worm.
Esenţa invenţiei constă în aceea că prin acţiunea alcoolului propargilic cu bromura 1-bromhexan în amoniac lichid se obţine substanţa nonin-2-ol-1 (1), care în prezenţa amidurii de sodiu şi etilendiamină se transformă în alcoolul nonin-8-ol-1 (2) cu legătura acetilenică terminală. Protecţia grupei hidroxile în alcoolul (2) cu 2,3-dihidropiran duce la acetalul 1-(21-tetrahidropiraniloxi)-8-nonin (3), care după reacţia cu bromura de propil se transformă în 1-(21-tetrahidropiraniloxi)-dodecin-8 (4). După deprotejarea grupei hidroxile (16% acid sulfuric, etanol) se obţine alcoolul acetilenic dodecin-8-ol-1 (5), reducerea căruia în prezenţa catalizatorului de Ni cu etilendiamină în alcool etilic duce la cis-8-dodecenol-1 (6). Prin acetilarea alcoolului (6) cu clorură de acetil în benzen în prezenţa piridinei se obţine cis-8-dodecenilacetatul (7) - componentul principal al feromonului sexual al viermelui prunelor, care a manifestat activitate biologică înaltă în condiţii de câmp. The essence of the invention is that by the action of propargylic alcohol with 1-bromohexane bromide in liquid ammonia, the substance nonin-2-ol-1 (1) is obtained, which in the presence of sodium amide and ethylenediamine is transformed into the alcohol nonin-8-ol- 1 (2) with the terminal acetylenic bond. Protection of the hydroxyl group in alcohol (2) with 2,3-dihydropyran leads to the acetal 1-(21-tetrahydropyranyloxy)-8-nonine (3), which after reaction with propyl bromide is transformed into 1-(21-tetrahydropyranyloxy)- dodecin-8 (4). After deprotection of the hydroxyl group (16% sulfuric acid, ethanol), the acetylenic alcohol dodecin-8-ol-1 (5) is obtained, the reduction of which in the presence of the Ni catalyst with ethylenediamine in ethyl alcohol leads to cis-8-dodecenol-1 (6 ). By acetylating alcohol (6) with acetyl chloride in benzene in the presence of pyridine, cis-8-dodecenyl acetate (7) is obtained - the main component of the sex pheromone of the plum worm, which showed high biological activity under field conditions.
Schema de sinteză: Synthesis scheme:
HC≡CCH2OH → C6H13C≡CCH2OH (1) → HC≡CCH2OH → C6H13C≡CCH2OH (1) →
HC≡C(CH2)7OH (2) → HC≡C(CH2)7OR (3, R= tetrahidropiranil) → HC≡C(CH2)7OH (2) → HC≡C(CH2)7OR (3, R= tetrahydropyranyl) →
C3H7C≡C(CH2)7OR (4) → C3H7C≡C(CH2)7OH (5) → C3H7C≡C(CH2)7OR (4) → C3H7C≡C(CH2)7OH (5) →
C3H7CH=CH(CH2)7OH (6) → C3H7CH=CH(CH2)7OCOCH3 (7) C3H7CH=CH(CH2)7OH (6) → C3H7CH=CH(CH2)7OCOCH3 (7)
Rezultatul tehnic obţinut cu ajutorul procedeului propus se datoreşte faptului că în sinteza cis-8-dodecenilacetatului se foloseşte regruparea legăturii triple în alchilderivatele alcoolului propargilic, ce simplifică şi ieftineşte procesul de sinteză şi permite obţinerea feromonului sexual cu puritate izomerică şi activitate biologică la nivel cu martorul. The technical result obtained with the help of the proposed procedure is due to the fact that in the synthesis of cis-8-dodecenyl acetate, the regrouping of the triple bond in the alkyl derivatives of propargylic alcohol is used, which simplifies and cheapens the synthesis process and allows obtaining the sexual pheromone with isomeric purity and biological activity at the level of the control .
Exemple de realizare a invenţiei Examples of realization of the invention
Exemplul 1. Example 1.
Nonin-2-ol-1 (1). Într-un balon de 1,0 L cu agitator, deflegmator şi picurătoare se toarnă 0,8 L amoniac lichid, se adaugă puţin nitrat de fier(III), apoi în porţii mici se adaugă 7 g (1,0 mol) litiu metalic. După 30 min se adaugă 28,0 g (0,5 mol) alcool propargilic. Peste 2 ore se picură 62,7 g (0,38 mol) bromură de hexil în 150 mL tetrahidrofuran, se amestecă 2…3 ore şi se lasă peste noapte. A doua zi se amestecă 2 ore, apoi se adaugă clorură de amoniu pentru a descompune produsul reacţiei, se diluează cu apă şi se extrage cu eter. Stratul organic se spală şi se usucă pe Na2SO4. S-au obţinut 37,2 g substanţă (70%) cu temperatura de fierbere (t.f.) 115…120°C/2 mm Hg. Nonin-2-ol-1 (1). In a 1.0 L flask with a stirrer, dephlegmator and dropper, pour 0.8 L of liquid ammonia, add a little iron(III) nitrate, then add 7 g (1.0 mol) of metallic lithium in small portions . After 30 min, 28.0 g (0.5 mol) of propargylic alcohol is added. Over 2 hours, drop 62.7 g (0.38 mol) of hexyl bromide in 150 mL of tetrahydrofuran, mix for 2...3 hours and leave overnight. The next day, stir for 2 hours, then add ammonium chloride to decompose the reaction product, dilute with water and extract with ether. The organic layer is washed and dried over Na2SO4. 37.2 g of substance (70%) with boiling point (m.p.) 115...120°C/2 mm Hg were obtained.
Exemplul 2. Example 2.
Nonin-8-ol-1 (2). Într-un balon de 1,0 L cu agitator se obţine amidură de sodiu (din 18,1 g sodiu în amoniac lichid). După aceasta se evaporă 70% din amoniac şi se adaugă repede 390 mL etilendiamină. În continuare, amestecul reactant se încălzeşte până la 80°C şi se agită 15 min, se răceşte până la 60°C şi se adaugă 36,4 g (0,26 mol) nonin-2-ol-1 (1), amestecul reactant se încălzeşte. După adăugarea alcoolului se agită 20 min, apoi se agită la 80°C 4…6 ore. Sfârşitul reacţiei se determină conform cromatografiei pe strat subţire. Produsul reacţiei se descompune cu apă, se extrage cu eter, se prelucrează cu apă, se usucă stratul organic şi se distilează. S-au obţinut 21,9 g substanţă cu t.f. 90…115°C/2 mm Hg. Nonin-8-ol-1 (2). In a 1.0 L flask with a stirrer, sodium amide is obtained (from 18.1 g of sodium in liquid ammonia). After this, 70% of the ammonia evaporates and quickly add 390 mL of ethylenediamine. Next, the reaction mixture is heated to 80°C and stirred for 15 min, cooled to 60°C and 36.4 g (0.26 mol) nonin-2-ol-1 (1) is added, the mixture reactant heats up. After adding the alcohol, stir for 20 min, then stir at 80°C for 4...6 hours. The end of the reaction is determined according to thin layer chromatography. The reaction product is decomposed with water, extracted with ether, processed with water, the organic layer is dried and distilled. 21.9 g of substance were obtained with m.p. 90…115°C/2 mm Hg.
Exemplul 3. Example 3.
Dodecin-8-ol-1 (5). Într-un balon de sticlă de 1,0 L cu agitator, picurătoare şi răcitor cu tub cu KOH se toarnă 800 mL amoniac lichid, se adaugă nitrat de fer (III) şi 2,4 g litiu (0,35 mol) în porţii mici. După obţinerea amidurii de litiu încet se adaugă 33,6 g (0,15 mol) alcool acetilenic (2) protejat cu dihidropiran (substanţa 3, obţinută din nonin-8-ol-1 şi dihidropiran în prezenţa HCl conc. la 20°C) şi se amestecă 2 ore. Apoi se picură 16,2 g (0,15 mol) bromură de propil în 40 mL tetrahidrofuran, se amestecă 2…3 ore şi se lasă peste noapte. A doua zi se amestecă 2 ore, se adaugă clorură de amoniu, 200 mL eter, se evaporă amoniacul şi se descompune cu apă. Stratul organic se separă, se spală cu apă şi se usucă. Se evaporă solventul, se deprotejează grupa OH (16% acid sulfuric, etanol), se distilează solventul, iar reziduul se distilează în vid. S-au obţinut 16,3 g (60%) dodecin-8-ol cu t.f. 85…90°C/1 mm Hg cu puritatea de 93%. După purificare pe coloană cu silicagel s-au obţinut 15,4 g substanţă cu puritatea de 98%, spectrul-IR, cm-1: 2244, 3100…3600. Dodecin-8-ol-1 (5). Pour 800 mL of liquid ammonia into a 1.0 L glass flask with stirrer, dropper and tube condenser with KOH, add iron(III) nitrate and 2.4 g of lithium (0.35 mol) in portions small. After obtaining the lithium amide, slowly add 33.6 g (0.15 mol) of acetylenic alcohol (2) protected with dihydropyran (substance 3, obtained from nonin-8-ol-1 and dihydropyran in the presence of conc. HCl at 20°C ) and mix for 2 hours. Then drop 16.2 g (0.15 mol) of propyl bromide in 40 mL of tetrahydrofuran, mix for 2...3 hours and leave overnight. The next day, mix for 2 hours, add ammonium chloride, 200 mL of ether, evaporate the ammonia and decompose with water. The organic layer is separated, washed with water and dried. The solvent is evaporated, the OH group is deprotected (16% sulfuric acid, ethanol), the solvent is distilled, and the residue is distilled under vacuum. 16.3 g (60%) of dodecin-8-ol were obtained with t.p. 85...90°C/1 mm Hg with 93% purity. After purification on a silica gel column, 15.4 g of substance with a purity of 98% were obtained, IR spectrum, cm-1: 2244, 3100...3600.
Exemplul 4. Example 4.
Cis-8-dodecen-1-ol (6). Într-un balon de 0,25 L se introduc 1,9 g acetat de nichel şi 32 mL alcool etilic, se suflă sistemul cu hidrogen şi cu o seringă la agitare se introduce soluţia de 0,3 g borhidrură de sodiu în 15 mL alcool etilic, 0,9 mL etilendiamină şi 14,6 g (0,08 mol) dodecin-8-ol în 30 mL alcool etilic. Se amestecă până la încetarea absorbirii hidrogenului. Sfârşitul reacţiei se controlează cu ajutorul cromatografiei gaz-lichid. După terminarea reacţiei se distilează în vid şi se obţin 11,8 g (80%) substanţă cu t.f. 80…95°C/1 mm Hg, spectrul-IR, cm-1: 1050, 1640, 3640. Cis-8-dodecen-1-ol (6). 1.9 g of nickel acetate and 32 mL of ethyl alcohol are introduced into a 0.25 L flask, the system is blown with hydrogen and with a syringe, while stirring, the solution of 0.3 g of sodium borohydride in 15 mL of alcohol is introduced ethyl alcohol, 0.9 mL ethylenediamine and 14.6 g (0.08 mol) dodecin-8-ol in 30 mL ethyl alcohol. Mix until hydrogen absorption stops. The end of the reaction is controlled using gas-liquid chromatography. After the end of the reaction, it is distilled under vacuum and 11.8 g (80%) of substance with t.f. 80...95°C/1 mm Hg, IR spectrum, cm-1: 1050, 1640, 3640.
Exemplul 5. Example 5.
Cis-8-dodecenilacetatul (7). Într-un balon se plasează 11 g (0,06 mol) cis-8-dodecenol, 110 mL benzen şi 5,7 g (0,072 mol) piridină. La amestecare şi la temperatura camerei se adaugă 5,7 g (0,072 mL) clorură de acetil. Se amestecă 3 ore la 50°C, se controlează mersul reacţiei cu ajutorul cromatografiei pe strat subţire. După sfârşitul reacţiei produsul obţinut se descompune cu apă, stratul de eter se spală cu o soluţie concentrată de hidrogencarbonat de sodiu, apoi cu apă şi se usucă reziduul cu sulfat de sodiu. Solventul se evaporă şi se distilează în vacuum. Se obţin 11,5 g (85%) acetat cu t.f. de 90…100°C/1 mm Hg, nd 20 1,4654, spectrul-IR, cm-1: 1030, 1230, 1640, 1735, 2985. Cis-8-dodecenyl acetate (7). 11 g (0.06 mol) cis-8-dodecenol, 110 mL benzene and 5.7 g (0.072 mol) pyridine are placed in a flask. With stirring and at room temperature, 5.7 g (0.072 mL) of acetyl chloride is added. Mix for 3 hours at 50°C, control the progress of the reaction with the help of thin layer chromatography. After the end of the reaction, the obtained product is decomposed with water, the ether layer is washed with a concentrated solution of sodium bicarbonate, then with water and the residue is dried with sodium sulfate. The solvent is evaporated and distilled under vacuum. 11.5 g (85%) of acetate with r.p. of 90…100°C/1 mm Hg, nd 20 1.4654, IR-spectrum, cm-1: 1030, 1230, 1640, 1735, 2985.
Conform materialelor cererii de invenţie, unul dintre avantajele procedeului este faptul că legătura triplă în procedeul de obţinere a cis-8-dodecenilacetatului se introduce prin utilizarea alcoolului propargilic (care este de zeci de ori mai ieftin ca hidrocarbura pentin-1), şi anume: se obţine alchilderivata alcoolului propargilic cu legătura triplă în poziţia 2 - în acest caz nonin-2-ol-1 (1), care, mai apoi, în prezenţa amidurii de sodiu şi etilendiamină se transformă în alcoolul acetilenic nonin-8-ol-1 (2, substanţă-cheie în sinteza cis-8-dodecenilacetatului) cu legătura triplă (acetilenică) terminală, adică are loc regruparea legăturii triple în alchilderivatele alcoolului propargilic, care se utilizează cu succes în sinteza cis-8-dodecenilacetatului - feromonul sexual al viermelui prunelor. According to the materials of the application for invention, one of the advantages of the process is the fact that the triple bond in the process of obtaining cis-8-dodecenyl acetate is introduced by using propargylic alcohol (which is tens of times cheaper than pentyne-1 hydrocarbon), namely: the alkyl derivative of propargylic alcohol with the triple bond in position 2 is obtained - in this case nonin-2-ol-1 (1), which, later, in the presence of sodium amide and ethylenediamine, is transformed into acetylenic alcohol nonin-8-ol-1 (2, key substance in the synthesis of cis-8-dodecenyl acetate) with the terminal (acetylenic) triple bond, i.e. the regrouping of the triple bond occurs in the alkyl derivatives of propargylic alcohol, which is successfully used in the synthesis of cis-8-dodecenyl acetate - the sex pheromone of the worm plums.
1. Holan G. and O,Keefe D.F. An improved synthesis of insect sex attractant: cis-8-dodecen-1-ol acetate. Tetrahedron Letters, No 9, pp. 673-674, 1973 1. Holan G. and O, Keefe D.F. An improved synthesis of insect sex attractant: cis-8-dodecen-1-ol acetate. Tetrahedron Letters, No. 9, pp. 673-674, 1973
2. Одиноков В.Н., Ишмуратов Г.Ю., Балезина Г.Г., Толстиков Г.А. Феромоны насекомых и их аналоги. XIII. Синтез (Е)- и (Z)-8-додеценилацетатов - компонентов половых феромонов Grapholitha funebrana и Grapholitha molesta. Химия природных соединений, № 3, с. 398-400, 1985 2. Одиноков В.Н., Ишмуратов Г.Ю., Balezina Г.Г., Толстиков Г.А. Insect pheromones and their analogues. XIII. Synthesis of (Е)- and (Z)-8-dodecenyl acetates - components of the sex pheromones of Grapholitha funebrana and Grapholitha molesta. Chemistry of natural compounds, № 3, p. 398-400, 1985
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3906035A (en) * | 1973-01-30 | 1975-09-16 | Commw Scient Ind Res Org | Process for the preparation of cis-8-dodecen-1-ol acetate |
| GB1504077A (en) * | 1975-07-08 | 1978-03-15 | Procida | Method for controlling cryptophlebia leucotreta using dodecenyl acetate |
| US4877891A (en) * | 1987-08-08 | 1989-10-31 | Basf Aktiengesellschaft | 1,1-dialkoxy- or 1,1-(alpha, omega-methylenedioxy)-non-2-yn-9-01 and their OH-protected derivatives |
| JPH08231304A (en) * | 1995-02-24 | 1996-09-10 | Norin Suisansyo Sanshi Konchu Nogyo Gijutsu Kenkyusho | Sex stimulant for yellow-spotted beetle |
| US6838576B1 (en) * | 2003-10-23 | 2005-01-04 | 3M Innovative Properties Company | Process for preparing functional group-containing olefinic compounds |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3906035A (en) * | 1973-01-30 | 1975-09-16 | Commw Scient Ind Res Org | Process for the preparation of cis-8-dodecen-1-ol acetate |
| GB1504077A (en) * | 1975-07-08 | 1978-03-15 | Procida | Method for controlling cryptophlebia leucotreta using dodecenyl acetate |
| US4877891A (en) * | 1987-08-08 | 1989-10-31 | Basf Aktiengesellschaft | 1,1-dialkoxy- or 1,1-(alpha, omega-methylenedioxy)-non-2-yn-9-01 and their OH-protected derivatives |
| JPH08231304A (en) * | 1995-02-24 | 1996-09-10 | Norin Suisansyo Sanshi Konchu Nogyo Gijutsu Kenkyusho | Sex stimulant for yellow-spotted beetle |
| US6838576B1 (en) * | 2003-10-23 | 2005-01-04 | 3M Innovative Properties Company | Process for preparing functional group-containing olefinic compounds |
Non-Patent Citations (4)
| Title |
|---|
| Holan G. and O,Keefe D.F. An improved synthesis of insect sex attractant: cis-8-dodecen-1-ol acetate. Tetrahedron Letters, No 9, pp. 673-674, 1973 * |
| Kenji Mori and Takuya Tashiro. Useful reactions in Modern Pheromone Synthesis. Current Organic Synthesis, 2004, 1, 11-29, Regăsit în Internet la 2013.06.24, url: http://benthamscience.com/cos/sample/cos1-1/Mori.pdf * |
| Kenji Mori. The Synthesis of Insect Pheromones, in The Total Synthesis of Natural Products, Vol. 4, 1981. Edited by John ApSimer vezi pag. 6, 9-10, 25-26 * |
| Одиноков В.Н., Ишмуратов Г.Ю., Балезина Г.Г., Толстиков Г.А. Феромоны насекомых и их аналоги. ХIII. Синтез (Е)- и (Z)-8-додеценилацетатов - компонентов половых феромонов Grapholitha funebrana и Grapholitha molesta. Химия природных соединений, № 3, с. 398-400, 1985 * |
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