DE2365939A1 - CYCLOPENTENE AND METHOD FOR PRODUCING IT - Google Patents

Description

July 19, 1976

Patent attorneys

_Dr Fr. «Lederer 2365939

6510/8 3-001

L. Givaudan & Cie Societe Anonyme, Vernier-Geneve (Switzerland)

Cyclopentenes and processes for their preparation

The invention relates to cyclopentene and a process for their preparation. The cyclopentene according to the invention have the formula

wherein R is hydroxy or lower alkoxy and

2
R is hydrogen, lower alkyl or lower

'alkylidene

represent and the dashed line means an optional bond.

609850 / 108S

The expression defines in the registration at the door "Lower" in connection with alkyl, alkoxy or alkylidene radicals Groups with up to 6 carbon atoms «

The invention also relates to the use of the compounds of the formula I as fragrances and fragrances of fkomposi · functions, characterized by a content of a compound of the formula I. -

Subgroups of compounds of the formula I according to the invention are described by the following formulas Ia and Ib

Yes

Ib

in which R and the dashed line have the meanings given above and R is a lower alkyl radical

The "inventive method is characterized in that a compound of the formula

■ 6Q9850 / 108S

II

in the presence of an acidic catalyst with an enol ether the formula

or a corresponding acetal of the formula

wherein R represents a lower alkyl radical and

R is hydrogen, lower alkyl or lower

alkenyl means

'converts, possibly a 3-isopropeny! compound obtained catalytically hydrogenated to the corresponding 3-isopropyl compound, an obtained aldehyde of the formula

III

to the corresponding acid of the formula

R ²

609850/1089

Yes

oxidized and, if desired, this into a corresponding one Ester of the formula '

• where Ir represents a lower alkyl group, convicted.

In the implementation according to the invention, it is advantageous to use the enol ether in excess, with about 3 equivalents sufficient. If the corresponding acetal is used instead of the enol ether, the yields are somewhat lower to get connections in. '. ...

The reaction takes place in the presence of an acidic catalyst. As catalytically active acidic agent used manzweckmässigerweise strong Mineralsaüren such as sulfuric or phosphoric acid, acid salts, such as "B", potassium bisulfate, pyridine hydrochloride or mercuric acetate, strong organic acids .as for example, p-toluenesulfonic acid ₈ oxalic acid and trichloroacetic acid, or Lewis acids such as "zinc chloride or boron rifluoride etherate. The concentration of the catalyst in the reaction mixture is expediently about Ο, ΟΙ-Ι, Ο? ^ Preferably about 0 _s l-0.3 ^.

• The reaction can be both performed without LösungsndLttel as "The solvents can, _like, hydrocarbons such as benzene, '^ toluene _hexane? Heptane, isooctane or petroleum ether can be used. According to a special execution, the solvent and / or the

609S5 "0 / 108S" "'' ■. ■

alcohol formed during the reaction is distilled off.

. ''; The reaction is preferably "at elevated temperature, for example above 50 ⁰ C, especially in the backflow • fceraperatur of the reaction mixture, carried out. It can be carried out under normal pressure as well as under positive pressure. The Vervrendung of an inert gas such as nitrogen or argon, is In a special embodiment, the reaction is carried out in an autoclave by heating under an inert gas to an internal temperature of about 150 ° C. The end of the reaction is indicated by a marked drop in pressure.

The catalytic hydrogenation of a 3-isopropenyl compound of formula III to the corresponding 3-isopropyl compound can in a known manner in the presence of, for example, a noble metal, preferably palladium or platinum, if necessary. on a suitable carrier, preferably on calcium carbonate or barium sulfate. ■

The oxidation of aldehydes of the formula in to the corresponding acids of the formula la can be carried out in a manner known per se, for example with Jones reagent (CrO ^ / HpSO.). As well .

can, the acids Ia in a known manner in the Lower alkyl esters of the formula Ib are converted.

. The compounds of the formula I are distinguished by particular fragrance properties, in particular by fresh, woody, camphor-like, spicy, sometimes also flowery, """ester-like or slightly sweet odor notes , or for perfuming technical and cosmetic products of all kinds, such as solid and liquid detergents, synthetic

609850/1089 '

Use detergents, aerosols, soaps, creams or lotions Find. . .

Suitable concentrations of the compounds obtainable according to the invention are when used as a fragrance in perfume co-positions $ 1-30, in finished products such as Shampoos, soaps, lotions, etc. about 0.001-1 ^.

The compounds of the formula I are also starting compounds for the production of products that also Have fragrance or flavor properties and can be used accordingly.

S088S0 / 1089

■ reaction scheme

III'-l

11

IV'-l

11

R ^-

R IV "-1

609850/1089

Compounds of the formula I in which R represents hydrogen or lower alkyl (i'-1 or »1" -I) ₁ can be converted, for example, into compounds of spirane or azulentyρ by the reaction sequence shown in the above scheme.

The cyclopentene of the formulas III ⁸ -1 or III "-1 can be prepared in a known manner from the compounds I ^! -1 or I" -1 by reaction with an organometallic compound _f, in particular with an alkali metal acetylide or with a Grignard compound the formula

MgHaI

where B7 is hydrogen or methyl and Hal is chlorine

or represents bromine,
can be obtained.

It is the case of the reaction with an acetylide required · the connection of the formula initially obtained

OH VI-I

wherein R is hydrogen or lower alkyl

2 ·

R has the meaning given above,

in a manner known per se "doh" in the presence of a Lindlar · Catalyst (Pd / CaCO ~ poisoned with PbO), catalytic partial & tt hydrogenate. ·

■ S098B0 / 10II "

The compounds of the formulas III'-1 or III "-1 can then be cyclized with dehydration to give the compounds IV'-1 or rV" -l. The dehydrating cyclization can be carried out in a manner known per se. Strong inorganic or organic protic acids such as sulfuric acid, phosphoric acid, p-toluenesulfonic acid or trichloroacetic acid, acid salts such as potassium bisulfate or Lewis acids such as tin tetrachloride, aluminum trichloride or boron trifluoride etherate are expediently used as cyclizing agents. Suitable solvents are, for example, aliphatic and aromatic hydrocarbons, which may optionally be chlorinated or nitrated, or ethers, such as benzene, toluene, hexane, heptane, isooctane, diethyl ether, dioxane and tetrahydrofuran. The reaction temperature may be about -30 ° to about 12O ⁰ C; it is preferably approximately between 0 ° and room temperature.

'As by-products in the cyclization of a compound of the formula III'-1 compounds of the formulas VII-I ■ and VIII-I arise

VII-I

VIII-I

in which R, R and R have the meanings given above '.have and ... .- ......

R ¹¹ 'represents C _1-6 AU clusters.

In the cyclization of compounds of the formula III "-1

609850/1089 '■

can be used in addition to the compounds of the formula IV-I compounds of the azul type of the formula V "-l in yields of up to about 70 ^ obtain.

Example 1 ■ _m .

15 drops of 85% phosphoric acid were added to a mixture, cooled in a laboratory autoclave, of 76 g of 3-isopropenyl-1-methyl-2-methylenecyclopentan-1-ol and 120 g of isopropenyl methyl ether. After gassing with nitrogen, the autoclave was brought to an internal ^{temperature of 150 ° in an ISO 0} oil bath and kept at this temperature until there was a significant drop in pressure (about 50-75 minutes). The reaction mixture was quenched by intensive cooling, solid potash was added and the mixture was concentrated under reduced pressure on a rotary evaporator. By fractional distillation over solid potash, 58 g (βΟ / ί) 3-iso-

propenyl-l-methyl - 2- (3-oxobutyl) -cyclopent-l-ene, bp. _{Λ m} = pn u _s ux

69772 °, nz = 1.4836, is obtained. The compound has a woody, camphor-like, ionic odor.

' Example 2

4 g of 3-isopropenyl-l-methyl-2- (3-oxobutyl) -cyclopent-l-ene were hydrogenated in 50 ml of ethyl acetate in the presence of 400 mg of palladium on calcium carbonate (5%). After uptake of one equivalent of hydrogen, the solution was filtered Gelite _s concentrated and distilled under high vacuum. 4 g of 3-isopropyl-1-methyl-2- (3-oxobutyl) -cyclopent-1-ene were obtained

^ -0.0O ₅ ^et 5 ⁷⁰ ° 4 = .1.4709, τΒ _η3Λ ^ _Μα = 1725, 1390/70 and 1170 cm . The compound has a woody _s "flowery odor.

609B50 / 108

Example 3

12 drops of 85% phosphoric acid were added to a mixture, cooled to -15 ° in a laboratory autoclave, of 76 g of 3-isopropenyl-1-methyl-2-methylenecyclopentan-1-ol and 72 g of ethyl vinyl ether. After gassing with argon, the autoclave was brought to an internal temperature of 150 ° in an oil bath at 180 °, which took about 15 minutes, and was kept at this temperature until a significant drop in pressure (about 100 minutes). The reaction mixture was then quenched, taken up in ether, washed with aqueous bicarbonate solution and water, the solution was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The crude product obtained as a yellow oil (110 g) was fractionated and yielded 61 g (68fo) of pure 2- (2-formylethyl) -3-isopropenyl-1-ynethyl-cyclopent-1-ene with woody,

on

earthy smell; _{Bp 0j2} = 64-65 °; n £ ^u = 1.4888: 1 ^^^ = 3080, 2725, 1725, 1642, 1440, 1370, 1060 and 895 cm- ¹ .

Example 4

3.6 g of 2- (2-formylethyl) -3-isopropenyl-1-methyl-cyclopen-i 1-en were hydrogenated in 80 ml of ethyl acetate in the presence of 500 mg of palladium on calcium carbonate (5S ^ ig). After taking up one equivalent of hydrogen, the solution was filtered through Celite, concentrated and subjected to short-path distillation under high vacuum. 2- (2-Forinylethyl) -3-isopropyl-1-methyl-cyclopent-1-ene had a fresh, woody odor obtained in quantitative yield, bp _{n nn} , about = 1.4703, ^ _Pilm ^ _max = 2740, 1728, 1470, 1335,

1368 and 1100 cm " ¹

609850/1089

Example 5

A solution of 25 g of 2- (2-forinylethyl) -3 - isopropenyl-1-methyl-cyclopent-1-ene in 1200 ml of acetone was treated with 55 ml of Jones reagent at -10 °. The brown reaction mixture was poured onto sodium bicarbonate solution, ether extraction, washing neutral with sodium bicarbonate, saturated sodium chloride solution and water, drying of the extract with magnesium sulfate and removal of the solvent under reduced pressure yielded 20 g (80%) of a pale yellow, oily crude product 15 g of pure 2- (2 ~ carboxyethyl) -3-isopropenyl-1-meth.yl-cyclopent-1-ene were obtained by distillation, b.p. _QQ = 102 °, ¹ ^ p ₁₁₁₁₁ ^{1 v} _aax = 3600-

2400, 1720, 1645, 1450, 1420, 1380, 1330, 1290, 1220, 1085, 945 and 900 cm ". The compound has a woody, spicy, slightly sweet and somewhat musty odor.

Example 6

A mixture of 2 g of 2- (2-carboxyethyl) -3-isopropenyl-methyl-cyclopent-1-ene, 150 ml of absolute benzene and 4 ml of dimethoxy-dimethylamino-methane was used for 5 hours Heated to reflux. The solution was concentrated and the residue obtained as red oil on 50 g of silica gel with hexane / ether (19: 1) chromatographed. 1.95 g ($ 91) of 2- (2-carbomethoxyethyl) -3-isopropenyl-1-methyl-cyclopent-1-ene were obtained obtain,

on

Kp. _OfO1 about 700, _n ™ _{= ls476l>} ir ^. ^ _{Β 5} 100, 1742, 1645,

1440, 1375, 1330, 1255, 1195, 1170, 1085, 1025, 990, 895 "and 840 cm" *. The compound has a flowery, woody, ester-like odor.

6098 50/1089

Example 7

15 drops of 85% phosphoric acid were added to a mixture, cooled to -30 ° in a laboratory autoclave, of 76 g of 3-isopropenyl-1-methyl-2-methylenecyclopentai-1-ol and 130 g of ethyl 1-propenyl ether. After gassing with nitrogen, the autoclave was ^{brought to an internal temperature of 150 ° in an ISO 0} oil bath, which took about 15 minutes, and was kept at this temperature until there was a significant drop in pressure (about 75 minutes). The reaction mixture was then quenched standards up in ether, washed with aqueous bicarbonate and water, the solution over anhydrous Magnesi ¹ ImSuIfat dried and concentrated under reduced pressure. The crude product obtained as a yellow oil (135 g) was fractionated and gave 64 g (67 $) of pure 2- (2-? Orayipropyl) -3-isopropenyl-l-methyl-cyclopent-l-ene with woody,

20th

• earthy, musty smell, Kp. _{Q 0Qr} . - 51 ° ,. n _ß = 1.4825,

^Xβ film ^{: v)} max ^{= 3} ° ⁹⁰ ' ²⁷³⁰ ' ¹⁷³ ^ ^l3 45, 1460, 1380 and 893 cm "" ¹ .

Example 8

Iu analogy to the manner described in Example 5 18 g of 2- (2-formylpropyl) -3-isopropenyl-1-methylcyclopent-1-ene were obtained to 2- (2-carboxypropyl) -3-isopropenyl-1-methyl-cyclopent-1-ene (Yield 13.2 g = 68 $) oxidized,

Max
1460, 1440, 1418, 1375, 1290, 1245, 940 and 895 cm "" ¹ . · The compound has a slightly woody, sour odor.

Example 9

In analogy to the procedure described in Example 6, 3.12 g of 2- (2-Carbo :: ypropyl) -3-isopropenyl-1-methylcyclopent-1-ene were obtained esterified. The oily crude product was on

60 98.5 0/1 089

100 g of silica gel with hexane / ether (95 ° 1) are chromatographed. After distillation in a high vacuum, 2.96 g (37 °) of pure 2- (2-carbomethozypropyl) -3-isopropenyl-1 -: ethyl-cyclopent-1-ene were obtained; Ep. _OfO2 = 70 °, ΐξ ° = 1.4728, IR _pill3 : >>. _aax = 3090, 1740, 1642, 1460, 1435, 1370, 1325, 1285, 1250, 1195, 1170, 1120, 1085, 1060, 1035, 990, 890, 835 and 765 cm " ^1. The compound has a caraphor-like odor.

- Example 10

According to the method described in Example 7, by reacting 30.4 g of 3-isopropenyl-1-methyl-2-methylenecyelopentan-1-ol with 50 g of methyl (3-methyl-1-butenyl) ether in Presence of 7 drops of 85% phosphoric acid 2- (2-formyl-3-methyl-butyl) -3-isopropenyl-1-methyl-cyclopent-1-ene

20 shown in 455% yield, bp. _{Q 0QC} - = 55-56 °, n ^ = 1.4808, IRp _ilm : ^ _max = 3080, 2725, 1725, 1642, 1460/40 _s 1390/70 and 890 cm * " - ¹ ·. The compound has a cedar, woody, vaguely floral odor. ".

Example 11

A mixture of 7.6 g of 3-isopropenyl-1-methyl-2-ynethylene cyclopentan-1-ol and 8.1 g of 1,1-dimethoxy-3-diethyl-3-13utene was in the presence of 100 mg of freshly prepared, dry pyridine hydrochloride under nitrogen in an oil bath of 100 ° heated for 15 hours with continuous removal of the resulting methanol. Bs was then at 150 ° for 7 hours heated and finally to a mixture of bis and. Ether The ethereal phase was poured with bicarbonate solution and water, dried with anhydrous magnesium sulfate and concentrated under reduced pressure after distillation of the oily crude product were 6.5 g of 2- (2-Forinjl = 5-methyl-2-butenyl) -3-isopropenyl ~ l-methjl-cjclopent-l-ea

20th
received, ^ ■ ₀ , ^ ξ% ^ ' > fa

3100, 2760, 1675, 1635, 1440, 1375, 1155, 1060 and 895 approx " ^1. The compound has a woody, flowery, fruity-sweet odor. ·

Example 12 Composition with a fancy blue note:

Calibrated parts 2- (2-carboniethoxyethyl) -3-isopropenyl- 100 y-undecalaeton $ 1 * 5 1-methyl-cyciopent-1-ene ■ '1000 n-Nonylaldehyde 1? 6 * 5 Lauric aldehyde lOfo * 5 co-n- undecylenealdehyde IO7S * 20th 4-Decen-l-al IQfo * 5 Jasmine abs. synthetic 100 Phenylethyl alcohol 100 Citronellol laevo 50 Linalool 30th Folrosia Givaudan 5 Storax oil. 15th 7-hydroxy-3 »7-dinethyloctane-1-al 100 Eugenol 25th Isobutyl salicylate 25th Isocamphylcyclohexanol 50 Vetivenol - 50 Ylang ylang 60 Äbsolue Mimosa. . 10 Heliotropin .20 Civette naturally defatted 1Of ₀ * 15th Ethylenbrassilat 5O7S * - ■ '_ 15th Ambrette musk ...
«- - -. .20. Bergamot Oil ■ . 100 Absolue Flouve odorante $ 20 - / . ·. - 70

* in phthalic acid diethyester 609850/1089

2365939 lavender oil cultive 100 Example Γ5 Mousse de Chene soluble 20th Composition type Fougere Resinoid labdanum . 20th Parts by weight Phenylethyl alcohol 100 Phenylethyl acetate ■ "· 50 Amyl salicylate 50 Resinoid Galbanum 10 Patchouli oil 20th p ~ tert. -Butyl ^ -methylhydrocinnamic acid aldehyde d 20 Elemi oil 20th Lemon oil Italian 40 Basil oil 5 Iinalool 40 Bergamot oil. . · 50 Bourbon vetiver oil 15th 2-Me thy lunde canal l? O * 20th n ~ Fndecylaldehyde lO ^ o * 20th Citronellol 50 Clove oil Zanzibar 20th 7-Hydroxy-3 »7-dimethyloetan-1-al 30th Absolue Plouve odorante 2öfo 100 2 ~ (2-formyl-3-ni "ethyl-2-butenyl) -3-isopropyl- enyl-1-methyl-cyclopent-lene , 200 1000

* in phthalic acid diethyester 609850/1089 "

Claims (1)

Patent institute 1. Process for the preparation of cyclopentene of the formula wherein R is hydroxy or lower alkoxy and .R hydrogen _} Klederalkyl or ITiederalkylidene represent and the dashed line means an optional bond, characterized in that a compound of the formula II OH in the presence of an acidic catalyst with an enol ether the formula ".. or a corresponding ketal of the formula 609850/108 9 ' R ~ wherein R represents a lower alkyl radical and R hydrogen, never the alkyl or lower alkenyl means converts, optionally a 3-isopropenyl compound obtained catalytically hydrogenated to the corresponding 3-isopropyl compound, an obtained aldehyde of the formula III to the corresponding acid of the formula Yes oxidized and, if desired, this into a corresponding ester of the formula Ib 609850/108 "5 wherein Ir represents a lower alkyl group, convicted. ... · 2. The method according to claim 1, characterized in that that phosphoric acid is used as the acid catalyst. 3 · The method according to claim 1, characterized. that pyridine hydrochloride is used as the acid catalyst will. . 4 · Process according to claims 1-3 »characterized in that a compound of formula II with ethyl vinyl ether is implemented. '5 · Process according to claims 1-3, characterized thereby-' draws that a compound of formula II with ethyl 1-propenyl ether is implemented. ■ ". ··· 6. The method according to claims 1-3 »characterized in that a compound of formula II with methyl (3-ethyl-1-butenylO-ether - is implemented. 7. The method according to claims 1-3, characterized in that a compound of formula II with 1,1-dimethoxy-3-diethyl-3 ~ butene is implemented. 8 · Method of perfuming products, thereby characterized in that one is a compound of the formula 609850/1089 wherein R is hydroxy or lower alkoxy and R is hydrogen, lower alkyl or lower alkylidene represent "and the dashed line I ■ means an optional bond, used. '■. 9, process for the production of new fragrance compositions, characterized in that "known fragrance co-positions" are a compound of the formula wherein R is hydroxy or lower alkoxy and H hydrogen, hioderalkyl or IT lower alkylidene :: · _: "; ■; .. _. : · Aarstellen and the dashed line ■■ line means an optional bond, or that a compound of the formula I is added with natural compounds suitable as a constituent of fragrance compositions or synthetic compounds or mixtures mixed. ¹ P. Fragrance compositions characterized by a content of a compound of the formula ■ i ³ 609850/1089 wherein R is hydroxy or lower alkoxy and ρ
R hydrogen, 2-lower al ± yl or IT-lower alkylidene and the dashed line means an optional bond ". 11. Use of a compound of the formula wherein R is hydroxy or lower alkoxy and R is hydrogen, lower alkyl or lower alkylidene represent and the dashed line means an optional bond, as a fragrance. '- 12?) A compound of the formula wherein R is hydroxy or lower alkoxy and ρ
R hydrogen, IT lower alkyl or lower represent alkylidene and the dashed line an optional bond means. 609850/1089 13. A compound according to claim 12 of the formula Yes wherein R is hydrogen, lower alkyl or lower alkylidene represents and the dashed line means an optional bond. 14 «A compound according to claim 12 of the formula Ib wherein R is hydrogen, half-alkyl or IT-lower-alkylidene and . '. Niederalkj »·! represent and the dashed drawn line means an optional bond. . • 'S 609850 / 1Ό89