PL112118B2 - Process for preparing novel derivative of trimethylcyclopentene - Google Patents
Process for preparing novel derivative of trimethylcyclopentene Download PDFInfo
- Publication number
- PL112118B2 PL112118B2 PL21912378A PL21912378A PL112118B2 PL 112118 B2 PL112118 B2 PL 112118B2 PL 21912378 A PL21912378 A PL 21912378A PL 21912378 A PL21912378 A PL 21912378A PL 112118 B2 PL112118 B2 PL 112118B2
- Authority
- PL
- Poland
- Prior art keywords
- trimethylcyclopentene
- subjected
- derivative
- ester group
- preparing novel
- Prior art date
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- YNEQKUWRFVQFPF-UHFFFAOYSA-N 1,2,3-trimethylcyclopentene Chemical class CC1CCC(C)=C1C YNEQKUWRFVQFPF-UHFFFAOYSA-N 0.000 title claims description 5
- 238000004519 manufacturing process Methods 0.000 title 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 125000004185 ester group Chemical group 0.000 claims description 5
- -1 2,2,3-trimethylcyclopenten-3-yl Chemical group 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 238000006546 Horner-Wadsworth-Emmons reaction Methods 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 229910052987 metal hydride Inorganic materials 0.000 claims description 3
- 150000004681 metal hydrides Chemical class 0.000 claims description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 238000009835 boiling Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000000284 extract Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- GGUBFICZYGKNTD-UHFFFAOYSA-N triethyl phosphonoacetate Chemical compound CCOC(=O)CP(=O)(OCC)OCC GGUBFICZYGKNTD-UHFFFAOYSA-N 0.000 description 2
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 1
- 241000723346 Cinnamomum camphora Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 229960000846 camphor Drugs 0.000 description 1
- 229930008380 camphor Natural products 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000012280 lithium aluminium hydride Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- YPPQYORGOMWNMX-UHFFFAOYSA-L sodium phosphonate pentahydrate Chemical compound [Na+].[Na+].[O-]P([O-])=O YPPQYORGOMWNMX-UHFFFAOYSA-L 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Przedmiotem wynalazku jest sposób wytwarzania nowej pochodnej trójmetylocyklopentenu, o wzorze przedstawionym na rysunku, znajdujacej zastosowanie jako skladnik kompozycji perfumeryjnych.Istota wynalazku polega na tym, ze l-(2,2,3- trójmetylocyklopenten-3-ylo)propanon-2 poddaje sie reakcji Wittiga-Hornera z karboalkoksymetylofosfonia- nem dwualkilowym. W wyniku powyzszej reakcji otrzymuje sie ester alkilowy, który poddaje sie selektywnej redukcji grupy estrowej, korzystnie przy uzyciu kompleksowych wodorków metali, a nastepnie estryfikuje azeotropowo kwasem mrówkowym.Zwiazek chemiczny, wytworzony sposobem wedlug wynalazku, zarówno w postaci racemicznej, jak i optycznie czynnej, ma trwaly zapach korzenno-drzewny.Zaleta sposobu jest stosowanie latwo dostepnego surowca, wytwarzanego z duza wydajnoscia z kamfory albo alfa-pienu.Przedmiot wynalazku jest objasniony w przykladzie wytwarzania nowej pochodnej trójmetylocyklopentenu, mrówczanu (E)-3-metylo-4-(2,2,3-trójmctylocyklopen- ten-3-ylo)buten-2-ylu, o wzorze przedstawionym na rysunku.Przyklad. 140 g (0,625 mola) karboetoksymetylofo- sfonianu dwuetylowego wkrapla sie do zawiesiny 15 g (0,625 mola) wodorku sodowego w 400 ml eteru absolutnego, w temperaturze 20°C, otrzymujac sodowa pochodna karboetoksymetylofosfonianu dwuetylowego.Roztwór sodowej pochodnej fosfonianu wkrapla sie do wrzacego roztworu 83,1 g (0,50 mola) l-(2,2,3-trójmety- locyklopenten-3-ylo)propanonu-2 w 600ml eteru, w ciagu 4 godzin, a nastepnie ogrzewa mieszanine reakcyjna do wrzenia przez kolejne 4 godziny. Po dodaniu 200ml wody produkt ekstrahuje sie eterem naftowym, a ekstrakty przemywa woda i suszy siarczanem sodowym. Surowy produkt saczy sie przez krótka kolumne z silikazelem (eluent-eter naftowy) i destyluje. Roztwór otrzymanego estru w 100ml eteru dodaje sie do zawiesiny 8,0 g (0,21 mola) wodorku litowo-glinowego w 300 ml eteru, w temperaturze 20°C.Po uplywie godziny mieszanine rozklada sie roztworem kwasnego winianu sodowego, ekstrahuje eterem, prze¬ mywa ekstrakty nasyconym wodoroweglanem sodowym i woda. Otrzymany surowy alkohol destyluje sie przez krótka kolumna otrzymujac 75 g produktu. 19,9 g (0,10 mola) otrzymanego zwiazku, 5,75 g (0,125 mola) kwasu mrówkowego oraz 50ml chlorku metylenu ogrzewa sie do wrzenia pod nasadka do azeotropowego usuwania wody, do momentu az woda przestaje sie zbierac.Nastepnie roztwór przemywa sie nasyconym roztworem weglanu sodowego, suszy siarczanem sodqwym i destyluje surowy produkt pod obnizonym cisnieniem. W wyniku powyzszego otrzymuje sie 20,0 g bezbarwnego, oleistego mrówczanu (E)-3-metylo-4-(2,2,3-trójmetylo- cyklopenten-3-ylo-)buten-2-ylu.Wlasnosci zwiazku, wytworzonego w powyzszym112118 przykladzie wykonania wynalazku, ilustruje ponizsza tabela.Temperatura lazni °C/kPa 126-128/ 1.333-10"' nwD IR(cm_l) 1.4785 3042 w 2957vs 1725vs(CO) l666w(C=C) 1460 s 1444 s 1383 s 1361 s 1160 vs(C-0) 800si=CH) PMR/Ó. HMDS, CC14) J*^ 2 . 6H. (CH?hC l,86szer.s. 3H, CHjC = l,99s,3H,CHJC=CHCH20 1,75-2.62 mult., 5H 4.86d.J = 7Hz.2H,=CHCHjO 5.42szer.s,lH,=CH(cykl.) 5.61 szer.i,J = 7Hz, 1H, =CHCH20 8.19 s, IH, CHO Uwagi E/Z =90:IO (glc) Zastrzezenia patentowe 1. Sposób wytwarzania nowej pochodnej trójmetylo- cyklopentenu, o wzorze przedstawionym na rysunku, znamienny tym, ze l-(2,2,3-trójmetylocyklopenten-3- ylo)propanon-2 poddaje sie reakcji Wittiga-Hornera z karboalkoksymetylofosfonianem dwualkilowym, po czym tak otrzymany ester poddaje sie selektywnej redukcji grupy estrowej, a nastepnie estryfikuje sie azeotropowo kwasem mrówkowym. 2. Sposób wedlug zastrz. 1, znamienny tym, ze w procesie redukcji grupy estrowej stosujesie kompleksowe wodorki metali. v^ CHPOCH Ptac. Pbligraf. UP PRL. Nakhd 120 egz.Cena 45 zl PLThe subject of the invention is a process for the preparation of a new trimethylcyclopentene derivative, with the formula shown in the figure, which can be used as an ingredient in perfumery compositions. Wittig-Horner with dialkyl carboalkoxymethylphosphonate. As a result of the above reaction, an alkyl ester is obtained, which is subjected to the selective reduction of the ester group, preferably with complex metal hydrides, and then azeotropically esterified with formic acid. The chemical compound prepared according to the invention, both in racemic and optically active form, has persistent spicy-woody smell. The advantage of the method is the use of easily available raw material, produced in high yield from camphor or alpha-foam. The subject matter of the invention is explained in the example of the preparation of a new derivative of trimethylcyclopentene, (E) -3-methyl-4- (2) formate. 2,3-trimethylcyclopenten-3-yl) buten-2-yl of the formula shown in the drawing. 140 g (0.625 mol) of diethyl carboethoxymethylphosphonate was added dropwise to a suspension of 15 g (0.625 mol) of sodium hydride in 400 ml of absolute ether at 20 ° C to obtain the sodium derivative of the diethyl carboethoxymethylphosphonate. A solution of sodium phosphonate solution 83 was added dropwise to boiling boiling solution. , 1 g (0.50 mol) of 1- (2,2,3-trimethyl-cyclopenten-3-yl) propanone-2 in 600 ml of ether for 4 hours and then the reaction mixture was refluxed for another 4 hours. After adding 200 ml of water, the product is extracted with petroleum ether and the extracts are washed with water and dried with sodium sulfate. The crude product is filtered through a short silica column (eluent-petroleum ether) and distilled. A solution of the obtained ester in 100 ml of ether is added to a suspension of 8.0 g (0.21 mol) of lithium aluminum hydride in 300 ml of ether at 20 ° C. After an hour, the mixture is decomposed with a solution of acid sodium tartrate, extracted with ether, ¬ washes the extracts with saturated sodium bicarbonate and water. The obtained crude alcohol was distilled through a short column to obtain 75 g of the product. 19.9 g (0.10 mol) of the obtained compound, 5.75 g (0.125 mol) of formic acid and 50 ml of methylene chloride are boiled under the azeotropic water removal cap, until no more water collects. saturated sodium carbonate solution, dried with sodium sulfate and distilled the crude product under reduced pressure. As a result of the above, 20.0 g of a colorless, oily (E) -3-methyl-4- (2,2,3-trimethyl-cyclopenten-3-yl-) buten-2-yl formate are obtained. the above 1112118 embodiment of the invention is illustrated in the table below: Bath temperature ° C / kPa 126-128 / 1.333-10 "'nwD IR (cm_l) 1.4785 3042 w 2957vs 1725vs (CO) l666w (C = C) 1460 s 1444 s 1383 s 1361 s 1160 vs (C-0) 800si = CH) PMR / Ó. HMDS, CC14) J * ^ 2. 6H. (CH · hC 1.86 wide s. 3H, CHjC = 1.99s, 3H, CHJC = CHCH20 1.75-2.62 mult, 5H 4.86dJ = 7Hz.2H, = CHCHjO 5.42ws, lH, = CH (cycl) 5.61 wide, J = 7Hz, 1H, = CHCH20 8.19s, IH, CHO Notes E / Z = 90: IO (glc) Claims 1. A process for the preparation of a new trimethylcyclopentene derivative of the formula shown in the figure, characterized by that 1- (2,2,3-trimethylcyclopenten-3-yl) propanone 2 is subjected to the Wittig-Horner reaction with dialkyl carboalkoxymethylphosphonate, then the ester thus obtained is subjected to the selective reduction of the ester group, and then esterified azeotropically with formic acid. 2. The method according to claim The process of claim 1, wherein the reduction of the ester group uses complex metal hydrides. v ^ CHPOCH Ptac. Pbligraf. UP PRL. Nakhd 120 copies Price PLN 45 PL
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL21912378A PL112118B2 (en) | 1978-08-09 | 1978-08-09 | Process for preparing novel derivative of trimethylcyclopentene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PL21912378A PL112118B2 (en) | 1978-08-09 | 1978-08-09 | Process for preparing novel derivative of trimethylcyclopentene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| PL112118B2 true PL112118B2 (en) | 1980-09-30 |
Family
ID=19999036
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PL21912378A PL112118B2 (en) | 1978-08-09 | 1978-08-09 | Process for preparing novel derivative of trimethylcyclopentene |
Country Status (1)
| Country | Link |
|---|---|
| PL (1) | PL112118B2 (en) |
-
1978
- 1978-08-09 PL PL21912378A patent/PL112118B2/en unknown
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