DE2048970C3 - Bicycle (2.2.1 (-heptane and tricyclo (2.2.1.0 to the power of 2.6) -heptane derivatives, process for their production and their use as odoriferous substances - Google Patents

Description

(Ib)

(IbI

(Ic)

(Ie)

wherein R ^{1 is} ethylidene or ethyl and R ^{2 is} C _r C ₅ alkanoyloxy, hydroxy or oxo, and mixtures of these compounds, the compounds of the general formula I b, where R ^{1 is} the ethylidene radical and R ^{2 is} a Alkanoyloxy radical means are excluded.

2. Process for the preparation of the bicyclo (2.2, l) -heptane and tricyclo (2.2, l, 0 ²⁶ ) -heptane derivatives according to claim 1, characterized in that 5-Äthylidcn-2 -norbornene of the formula

(H)

with a Q-CValkanecarboxylic acid of the general formula R ² - COOH, in which R ^{2 has} the above meaning, in the presence of a protonizing catalyst and, if desired, the esters thus obtained are hydrogenated and / or saponified in any order and, if desired, the alcohols thus obtained are oxidized ketones .

3. Use of the compounds of the general formulas la, 1b and Ic as fragrances.

The invention relates to bicyclo (2.2, l) -heplan- and ■ icyclo (2.2.1.0 '"Hieplanderivate the general in which R ^{1 is} ethylidene or ethyl and R ^{2 is} Ci-CyAlkanoyloxy, hydroxy or oxo, and mixtures of these compounds , whereby the compounds of general formula b prepared according to patent 2023687, in which R ¹ denotes the ethylidene radical and R ² denotes an alkanoyloxy radical, are excluded, as well as a process for the preparation of these compounds and their use as fragrances.

A process for the preparation of 2-alkylidene-norbornane compounds is already known from the earlier patent 20 23 687, in which a l-alkonyl-nortricyclene is used as the starting compound. In contrast, in the process according to the invention according to the preceding claim 2, a 5-ethylidene-2-norbornene is reacted with a C, -C ₅ -alkanecarboxylic acid in the presence of a protonizing catalyst and, if desired, the ester thus obtained is hydrogenated and or saponified in any order and, if desired, the alcohols obtained in this way are oxidized to ketones.

In the earlier patent, the intended use for the 2-Alkylidcn-norbornane derivatives described there stated that they are used as starting compounds for the production of organic intermediates, Medicines and agricultural chemicals are suitable and for manufacture and cleaning of 5-alkylidene-2-norborncn can be used via a use of those described there Nothing is said about derivatives as fragrances.

Derivatives of trieyclo (2.2.1, 0 ^2f ') -heptaneii (Nortricyclcne) and Bieyelo (2.2, l) -heptanes (Norbornanc) have been known for a long time, but such compounds have not found use as fragrances. Derivatives of this type are /. In U.S. Patent No. 55 documents 27 38 356. 33 45 419. in British Patent 7 17 010. in J. Anier. (hem. Soc. 89, 2563-2569 (1967). in J. Am. (hem. Soc. 82, 6362 to 6366 (1960), and in .1. Amer. (hem. Soc. 84, 3918 to 3925 (1962). These are alcohols, ethers and ketones, which smell like camphor and are very unpleasant and therefore could not find any use in the olfactory industry up to howling. It is therefore surprising that the new compounds of the formulas la, Ib and Ic have advantageous and unusual factorial properties. The smell of these compounds is very diverse. /. H. fatty, spicy, fruehlig, flowery, cilrus-like, hol / iu, mim and rose artiu. The new

Compounds can accordingly be used in the manufacture the most varied of fragrance compositions are used.

That the new compounds in an advantageous manner z. B. from the compounds of the USA patent 27 3X 356 lift off can be seen in Examples 12 to 16 below. Would in those examples the connections of the l-'formulas la. Ih or Ic through replaces the compounds known from that patent specification, the corresponding formulations would be used as odoriferous compositions »completely useless. With it a new chemical substance can be used as a fragrance, it is not sufficient, however, that they have advantageous olfactory properties exhibits: other characteristics. z. B. low Toxicity, as well as non-aggression towards the dullness, are also very important. The new connections of the formulas Ia, 1b and ic meet these conditions, which is all the more surprising. than out an article by S. Winslein. J. Amcr. Chem. Soc, 83, 1516 (1961) several derivatives sharing the same Have ring system as the new compounds of the formulas la, Ib and Ic have become known, which are aggressive to the skin and have considerable toxicity.

From Chem. Eng. News, 45, S7-97 (1967). it is known that norbornadiene in the presence of acids exists both in the form of the norbornyl and in the form of the tricyclene-Γ = tricyclo (2.2.1.0 ^{2 (} ') -hcptanyl -] carbonium ion.

It is also known (Chem. En ". News. 45, 95 [1967]; US Pat. No. 2,738,356) that norbornadiene can be reacted with organic acids in the presence of protonizing acids to form tricyelo (2.2, 1.0- ⁽ ' ) -heplyl- and Norborncnyldcrivalen can be implemented.

In the presence of protonizing acids, ethylidene norbornene is a mixture of carbonium ions before, which react with organic acids, forming an ester mixture. It is known, that in addition reactions of the norbornadiene system in each case the thermodynamically less stable one Endoisomecre is formed, which is then partially rearranged into the more stable exoisomer.

The present invention accordingly provides an easily accessible way to get away from the cheap, Ethylidene norbornene obtained in the petrochemical industry from to arrive at derivatives of norbornane and nortricyclicn. The new derivatives are consequently cheap fragrances.

The compounds according to the invention (apart from the ketones) can, as will be shown below, in the undo and exo forms are available.

1- / H

R ^:

ciido e \ o

(l'ii)

eiuio exo

fl'h)

endo exo

(Ic)

The new compounds of the formulas la. Ib and Ic saponification of the primarily obtained lister in any

can be obtained by reacting 65 order, and if desired oxidation of the

5 -Athyliden - 2 - noiboinen with a C | -C _s -alkane- obtained alcohols to ketones. The following rcak-

carboxylic acid in the presence of a prolonization scheme illustrates the implementation of the new

Catalyst, if desired hydrogenation and / or Es'lcr:

OOCR H

(IV)

OOCR

(VJ)

OOCR

(VII)

(VIII)

The process according to the invention usually produces a mixture of the esters (the compounds of the formulas III to VIII), ie endo- and exo-6-ethyl-tricycio (2,2.1, 0 ^{2 <} > hepl-3-yl-cster (III and IV) and the endo- and exo-S-Ethylidcnnorborn ^ - and -3-yl esters (V. VI, VII, VIII) obtained.

In addition to the reaction outlined above, a side reaction takes place, whereby the esters V. VI, VII and VIII are partially further protonized and with an additional mole of the organic Acid react, with the formation of Diacyloxycstern, from which, however, by heating, z. B. in distillation, again the Monocytes Vl, VII and VIII are receded

OOCR

(V, VI.VII. VIII) OOCR

OOCR

+ RCOOH
(V. Vl. VIl. VIII)

Another mixture of esters can be obtained by hydrogenating the above mixture of the esters of the formulas III, IV, V, VI, VII and VI 11. From the reaction mixture thus obtained, the endo- and exo-6-ethyItricyclo (2.2, l, 0 ^2e ') -hcpt-3-yl-ester (IH and IV) can be recovered unchanged, while the endo- and exo-S-Ethylidcnorborn ^ - and -3-yl-esters (V, Vl, VII , VIII) have the corresponding endo- and exo-5-EthyI-norhorn-2- and -3-yl-Estcr (IX, X, Xl and XII) ücbildct. Their formulas are the following:

OOCR

OOCR

(IX)

OOCR

RCOOH

-Ι

Ο OCR

OOCR

(Xl)

/ YlIl

ic preparation of the mixture of the alcohols and ketones according to the invention can be shown schematically as be ordered:

O C)

C) OCR

O OCR

/ M

(IV)

C) OCR

0OCR

(VI)

C) OCR

OOCR H

(VI)

(VIII)

LvJ OOCR ⁺

(Ul)

(IV)

OOCR

OOCR

OOCR

(X)

OOCR

OOCR

(XII)

(XXI)

(XXIV)

[O]

OU

(XIII)

NaOH

OH

OH H

(XV)

(XVI)

OH

CKVII)

(XVIII)

H,

OH

OH

(XIII)

(XlV)

NaOH

OH

(XIX)

H
OH

^{/ X} V

(XX)

OH

OH

(XXI)

(XXII)

C)

(XXIlI)

(XXIV)

(XXV)

IO

3 °

35

A mixture of alcohols is formed by saponification of the esters III, IV, V, VI, VII, VIII: ₅ endo- and exo-6-ethyltricyclo (2.2, l. () ^{2 ft} ) -hcptane-3 are formed -ol (XIII, XIV) and endo- and exo-5-ethylidene norborn-2-and-.VoI (XV. XVI. XVII, XVlII).

Another mixture of alcohols is produced by saponification of the mixture of partially hydrogenated esters III. IV, IX, X, XI and XII: endo- and exo-6-ethyltricyclo (2,2, l, 0 ^{2 (} ') -heptane-.VoI (XIIl.XIV) and endo- and exo-5 are formed -Ethylnorborn-2- and -.VoI (XIII, XIV) and endo- and exo-5-ethylnorborn-2- and -3-ol (XIX. XX. XXL XXII).

A mixture of ketones is produced by the oxidation of the alcohol mixture. XIX. ΧΧ, ΧΧΙ and XXIl. a mixture of 6-ethyl-tricyclo (2.2.1, 0- ") -hcptan-3-one is formed (XXIII) and 5-Ethylnorbornan-2- and -3-one (XXlV) and (XXV).

For the corresponding conversion of ethylidene norbornene with organic acids any protonating acid, e.g. B. formic acid, sulfuric acid. Phosphoric acid. Toluenesulfonic acid, boron trifluoride. Boririfluoridätherat, Borlrifluoridhydrat or acidic resins serve as a catalyst. If ethylidene norbornene is reacted with formic acid, can the addition of a catalyst can be dispensed with.

The amount of catalyst is not critical. Preferably 1 to 5% based on the amount of the organic acid used, but it can also be only 0.1%. or on the other hand too 50% are used. With small amounts of catalyst, on the other hand, the reaction rate is reduced, i.e. the reaction time is lengthened: on the other hand, large amounts of catalyst probably reduce the reaction time, however, make the process uneconomical.

The ratio of organic acid to ethylidic norbornene is not critical. However, a large excess of organic acid favors the reaction process. Accordingly, 1 to 5 moles of organic acid are preferably used per mole of ethylidene norbornomine used.

The reaction temperature is also not critical. Temperatures of 20 (or below lead to long reaction time. during temperatures of 150 C z. B. lead to poor yields. if the The preferred conditions given above are adhered to, it has proven to be advantageous to adjust the reaction temperature in a range of 50 to 100 ° C.

The conditions for the saponification of the esters are also not critical. You can get this reaction according to methods known per se, for. B. Heating the esters to reflux in the presence of * äßri <: cm or alcoholic sodium or potassium fivdroxide. execute.

45

55

60 The conditions for the hydrogenation of the esters or alcohols are also not critical. One came to work in the absence or presence of a solvent. Suitable solvents are ζ. Β benzene. Toluene or alcohols. One works with advantage in the presence of a catalyst, e.g. B. I Wu 5 "· '" Raney-Niekel or 1 to 2% 5% palladium on activated carbon. The water pressure in the hydrogenation can be, for example, 3.4 to 17 Alm. And the temperature is in a range from 50 to 150 C move.

The conditions for the oxidation of the alcohols to the corresponding ketones are not critical; one can work according to the methods of alcohol oxidation which are known per se. Can be used as an oxidizing agent z. B. Sodium dichromal, sulfuric acid as the oxidation catalyst. The temperature range for this system z. B. 30 to 50 C.

The compositions of the present invention have unusual odor properties and accordingly pose valuable fragrances. The individual components of the mixtures can be removed by vacuum distillation isolated graze and have very interesting olfactory properties. The process products are also valuable as intermediate products for the production of other fragrances.

The structures of the individual components of the mixtures were established on the basis of the chemical Realizations, thermodynamic overlaps and the physical data obtained, e.g. B. gas chromatographic data. IR spectrum and NMR spectrum.

In the following examples, the temperatures are in degrees Celsius.

example 1

6-Aihyliricyelo (2.2.!. 0 ^: '') -hepl-3-yl-aeeiat and
5-ethyidene-norborn-2- and -3-yl-acetate

In a reaction vessel with a stirrer. Thermometer. Dripping funnel and cooler are equipped 180 g of acetic acid. 6 g of sulfuric acid (96%) and 1 ml of water are added. The mixture is stirred heated to 50 and then 120.4 g of ethylidene norbornene added at this temperature over a period of 30 minutes with slight cooling. The mixture is kept at 60 for 3 hours with stirring. 300 ml of water and 100 ml of benzene are then added and stir again for 5 minutes. The layers formed are then allowed to separate. The lower one, separated, acidic layer is with 3ma! 50 ml of benzene extracted. The benzene extracts are combined and washed three times with 50 ml of water each time and then with the aid of 10% sodium bicarbonate solution neutralized. The benzene is distilled off under reduced pressure. being 171.5 g of crude ester lag behind. The crude product is then vacuum des'.iüieri at 6 Torr in a 27 cm glass body column. whereby the following fractions are obtained:

(1) 12 g of boiling point 26 to 84 6 torr.

(2) 121 g of ester, boiling point 84 to 8 ^ 6 torr.
(31 16 g ester with a boiling point of 88 to 95 6 Torr.

Residue 14 g.

The 121 ü 1-SkT of the above faction 2 are at 5 Torr redistilled as described above, with the following:

(1) 14 g lister with a boiling point of 81 to 83/5 Torr,

(2) 106 g of ester with a boiling point of 83 to 94/5 torr,
Residue 1.5 g.

By redistillation of fractions 1 and 3 of the first distillation together with fraction 1 of the / wide distillation 25.2 g of product are obtained. These are combined with fraction 2 from the second distillation. The overall yield is accordingly 131.2 g (72.2% of theory) of the desired End product that has the following physical data:

(D 8.9% (2) 28.3% (3) 6.4% (4) 12.0% (5) 44.4%

By saponification of the reaction mixture obtained from Älhylidcnnorbornen and acetic acid in In the presence of a protonic acid catalyst, a mixture of alcohols is obtained which, as by gas chromatography can be shown, consists of 5 components:

(D 11.1%, (2) 35.1%, (3) 3.0%, (4) 40.5%, (5) 10.3%.

Saponification range 307.7, «>," = 1.4737,
spec. Weight 1, OI27 / 25 "/ 25").

The product has a green, greasy citrus odor on (peach note).

The 1R spectrum of the mixture shows a broad band at about 5.72, which is typical of the Carbonyl group of an ester, at about 8 μ the aceloxy band appears. The NMR spectrum shows the typical signals for the methyl and acetyl groups.

Gas chromatography (150 °) can produce 5 components can be determined in the mixture:

The reaction product obtained by the hydroboration of ethylidene norbornene corresponds to the above Component 4. By hydrogenating the above alcohol mixture it can be shown that components 3, 4 and 5 are hydrogenated. There arises a Reaction mixture which, according to gas chromatography, consists of the following 4 components:

(1) 7.0% (2) 26.6% (3) 48.2% (4) 18.2%

3 °

By hydrogenating the mixture obtained in this example it can be shown that the above components 1 and 2 are not hydrogenated and therefore they must be ethyl tricyclo (2.2, 1.0 ² - ^t ') -heptyl derivatives. while components 3, 4 and 5 are unsaturated and can therefore be hydrogenated to saturated esters. Components 3, 4 and 5 are accordingly ethylidic norborny derivatives.

(Components 3 and 4 are the hydrogenation products of components 3, 4 and 5 above.) Oxidation of the mixture of hydrogenated alcohols results in a mixture of ketones, 96.4% of which is obtained from a mixture of 2 ketones (13 , 8% and 82.6%) and another ketone (2%). These data show that the mixture consists mainly of two pairs of cndo- and exo-isomers, an ethyltricyclo (2,2,1,0 ^2f ') -heptyl pair and an ethylnorbornyl pair, as well as a small amount of ethylnorbornyl pair .

The mixture of acetates can be prepared by vacuum distillation with the aid of a Nester / Faust column be separated.

With regard to the five-component mixture described above further data can be seen in the following table.

Component I. Component 2 Component 4 Component 5 Component 3 Isomer Λ (II *) Isomer B (II) *) Isomer C (V) *) Isomer D (VI) *) Isomer U (IV) *) boiling point 76,575 torr 81.5 / 5 torr 85.575 torr 86.5 / 5 torr 83.075 torr Purity (VPC) 100% 100% 100% 100% 95% Reinheil **) 100% 100% 100% 100% 100% η 1.4610 1.4639 1.4780 1.4788 1.4791 "π C 73.26 73.25 73.24 73.18 73.29 "" H July 9 9.01 9.12 9.09 9.10 Calculated for C ₁₁ H ", ( "ο C 73.30 73.30 73.80 73.30 73.30 % H P.95 8.95 8.95 8.95 8.95

♦ l R CII,
• * l GerniiH saponification: s /; ihl.

The bands of the IR spectrum or the signals of the NMR spectrum of the isolated isomers are with the postulated structures compatible.

example

6-Ethyllricyclo (2,2,1.0 ^2l ') -hept-3-yl-propionate and
5-ethylidene norborn-2- and -3-yl propionate

In a reaction vessel equipped with a stirrer, thermometer, Drips richler and cooler is equipped, 444 g of propionic acid, 12 g of sulfuric acid (96%) and given 2 g of water. The mixture is heated to 60 with stirring and then over a A period of 30 minutes at this temperature, 240.4 g of atliylidene norbornene with slight cooling admitted. The mixture is kept at 60 for a further 5 hours with stirring. 6 (K) ml are then added Water and 200 ml of benzene are added and stirring is continued for 5 minutes. The layers are allowed to separate and separate the lower acidic layer off. This acidic layer is extracted with 2 times 50 ml of benzene. The Benzolexliakic are combined and then washed three times with 100 ml of water each time and then with the aid neutralized by IO% sodium bicarbonate solution. The benzene is distilled off under reduced pressure and receives 350 g of Rohcslcr. This crude product is at 3 Torr in a 37 cm glass body column distilled, resulting in the following fractions:

(1) 9.0 g from boiling point 68 to 82 "/ 3 torr.

(2) 285 g with a boiling point of 82 to 9 ^ / 3 torr,

(3) Uig ^ boiling point 95 to 108 73 lorr.
Residue 28 g.

The above fraction 2 (285 g) is dissolved in hexane and neutralized with 10% sodium carbonate solution. The aqueous layer is discarded, the hexane is distilled off from the organic layer and the residual material redistilled at 0.3 torr as described above. The following are obtained Parliamentary groups:

(1) 4.5 g. Boiling point 50 to 58 / 0.3 Torr,

(2) 16 ". Boiling point 58 to 62 0.3 torr,

(3) 24L5 g. Boiling point 62 to 64 / 0.3 Torr.

(4) 20g. Boiling point 66 to 70 OJ torr.
Residue 2.0 g.

Example 3

6-ethyltricyclo (2.2, 1.0, ² ") -hept-3-yl-butyrate and
5-Ethylidynnorborn-2- and -3-yl-butyrate

264.3 g of butleric acid. 6.0 g of sulfuric acid (96% strength | 1.0 ml of water and 120.2 g of ethylidic norbornene are reacted according to the information in Example 1. The amount of crude product (window flour is 195 g and is distilled according to the information in Example 2. 156.2 g is obtained . g. of the desired product boiling point of 73 / 0.5 Torr 10.8 g of boiling point 40 bi ^v 74 0.5 Torr and 18.5 g of residue the yield is therefore 75% and the analytical data are as follows...:

Saponification number 267.2: / 1 = 1.4700.

spec. Weight (25/25) 0.9796.

The product has a green, greasy and buttery odor. Gas chromatography (200 the following four components can be identified:

40

The redistillation of the fractions (namely 1 and 3 of the first distillation together with 1. 2 and 4 of the second distillation) delivers an additional 43.6 g of desired cm Product. The total yield (fraction 3) is accordingly 241.5 g plus 43.6 g = 285.1 g (61% of theory. The analytical data are as follows:

5 °

Saponification / ahl 287. Ji = 1.4728.
spec. Weight 125 2? ) 0.9923.

The product has a fresh, green, woody appearance Smell with notes of sassafras and anethole. <is the smell has a slightly fruity character.

4 components can be determined by gas chromatography (175):

(1) 8.2 "0 (21 25.0 ° 0 (31 15.4 ° η (41 51.4 ° "

(1) (2) (31 (4)

8.8%.
29.1%.
18.3%,
43.8%.

The IR spectrum shows
C'arbonvlbande and at 8.5

at 5.78 ■ /. a strong 1st biityrate gang.

A carbonyl band (at 5.75 μI as well as a propionate band (at 8.4 μ) can be detected in the IR spectrum. The NMR spectrum is also in agreement with the postulated structure.

Example 4

6-Athvhricyclo (2.2.l.0 ² ") -hept-3- \ i-isobut \ rai and
5-Alhylidene-norborn-2- and -3-vl-isobutyral

264.3g isobutleric acid. 6.0g sulfuric acid. in the Water and 120.2 g of ethylidene norbornene are reacted according to the information in Example 1. Mar receives 180 g of crude product (Fstergeinisch). Using vacuum distillation this crude product is purified according to the information in Example 2, with 131.8g (63.2 "ι. The theory) of the desired product Boiling point 63 to 65 0.6 lorr received, as well as 6.2 g from boiling point 50 to 67 and 0.6 torr 32.5 g residue. The analytical data are as follows:

Saponification number 266.7.11 1.4 ^ 50.
spe /. Weight (25 25 10.9730.

The smell of the product is green. IVuchiig-rosy. reminiscent of Geianylaeetat.

(iaseluomatographisch (I "5 I can 4 compo- | nenten lest.r. posted willow:

(21: see 4%.
131 IS.1%.
(41 43.9 °.,.

The IR "Specification of the product indicates 5.72
an (aibonylbandc on as well as at 8.3 and p.6
a broad doublet (isobutyraU

Example 5

6-Athvltricyclo (12.1.0 ^: ") -hept-3-yl-pi \ alai and
> Athyliden-norborn-2- and -3-yl-pi \ alal

306.4 g of pivalic acid c. 6.0 g sulfuric acid (1 (>% 1 1.0 ml water and 120.2 g ethylidene norbornene w or implemented according to the information in Example 1. I ■: 204 g of crude product are obtained (lislergemisehl Πιπνΐ

2593

Vacuum distillation as described in Example 2 gives 167 Nm (75.3% of theory) desired product from boiling point 67 to 6s) 0.5 Torr. 9.2 g of boiling point 33 to 72 0.5 Torr and 15.0 g residue.

Saponification number 245.1. η = 1.4645. spe /. Weight (25 25) 0.9521.

Gas chromatography (175 l becomes 3 components detected:

(M
(2)
(3)

15.5 "...

15.3 "« ..
69.2 ",,.

The product has an oily, floral odor with a hint of rose. The IR-Spekirum / cig! a siarke dog at 5.Xy. (Carbonyl) as well as a band at p.7 ■ ,. (Pivalal).

B e i s ρ i e 1 6

6-AthyUricyclo (2.2.1.0 ² ") -hept-3-yl-rormiai and 5-Alhyliden-norborn-2- and -3-yl-formate

In a reaction vessel. provided with stirrer. Thermometer. Add dropper and cooler to 70 g of 9S formic acid and heat to 70. 120 g of Athylidennorbornen are in a period of 10 minutes added, the mixture heated to 100 and at this temperature with stirring 4 ', held for hours. The reaction mixture is worked up as described in Example 1, 146 g of crude product are obtained. This Fslergeniisch is purified as in Example 2 by vacuum distillation, with 125.3 g (75.3 "(i of theory) of the desired product with a boiling point of 69 to 71 6 Torr as well as 13.3g of a Increase fraction from boiling point 3S to 76 6 Torr and 11.5 g of residue.

Saponification / ahl 327.3:; i = 1.4713.

Gas chromatography (150
nents can be determined:

can 4 compo-

(1) 7.9% (2) 62.0% (31 10.8% (4) 19.3%

indicated that the reaction mixture is filtered. 5 g of palladium (5% on charcoal) are added and two more hours at 7S and 3.4 atm hydrogen pressure is implemented. Fs does not find any vVassersloffaufnahme more stall. The catalyst is removed by filtration, and the crude product (99 g) is at 6 torr in a 37 cm column. filled with glass bodies, distilled. 95 g (94% the theory) of the desired product from boiling point 79 to 8376 Torr, as well as a fraction of 2.8 g of boiling point 76 to 85/6 Torr and 1.0 g of residue.

Saponification number 299.1, ni = 1.4607;
spec. Weight (25/25) 0.9925.

Gaschromatographiseh (150) 5 components can be found ^1:

i ¹

30th

35

40

55

The smell of the product can be characterized as green, furry, spicy, woody-campherarl-like. similar to coriander.

The IR spectrum shows a carbonyl band at 5.8Oy as well as a normal band at 8.5 y.

B e i s ρ i e 1 7

6-Älhyllricyclo (2.2.1.0 ² ") -hept-3-yl-acetal and 5-ethyl-norborn-2- and -3-yl-acelal

I (K) g. a mixture of a US 6-Älhy Il rieyclo (2,2,1.0 ² '') -hepl-3-yl-aceial and 5-Athylidennorborn-2- and -3-ylacelal (Example 1) feed in healing property of 10 g Raney Nickel hydrogenated at 78 and 2.7 to 3.4 atm hydrogen pressure in a Parr bomb, which requires a reaction time of 2 hours. The hydrogen taken up corresponds to 0.298 mol. The mixture is 54% hydrogenated, which means that 5-ethylidene norborn-2- and -3-yl-aetate is hydrogenated to the corresponding 5-ethylnorborn-2- or -3-yl-acelal have been. The complete llvdrieriiim is

(D 9.7% (2) 30.0% (3) 36.6% (4) 15.8% (5) 7.9%

The smell of the product is spicy, reminiscent of anise, woody (pine), camphcrähnlic'i with thujone character.

In the IR spectrum, the carbonyl band is found at 5.75 μ and the acetate band at 8.1 μ.

Example 8

6-Ethyltricyclo (2,2, 1,0 ² ' ⁽ ') -hcpt-3-yl-propionate and S-ethyl-norborn ^ - and -3-yl-propionate

233 gcincs mixture of 6-Ä'.hyl-lricyclo (2,2.1,0 ^{2 (>} ) -hcpt-3-yl-propionate and 5-ethylidene norborn-2- and -3-yl-propionate (prepared according to Example 2) are hydrogenated in the presence of 5 g of 5% palladium on carbon at 60 to 70 ^r, where the hydrogen pressure is maintained at 2.7 to 3.4 atm. After 5 hours the Wassersloffaufnahmc is completed. the Wasscrsloffaufnahmc entsprich ¹ 1,04MoI hydrogen , the mixture is 86% hydrogenated, which means that 5-ethylidene norborn-2- and -3-yl-propionate have been hydrogenated to the corresponding S-ethyl-boron-3-yl-propionate, respectively is filtered, the filter cake is washed with benzene and the benzene is removed under reduced pressure. The crude product (233 g) is distilled at 6 torr in a 37 cm column filled with glass bodies. 231.7 g (97.6% of the Theory) of the desired product from boiling point 99 to 10176 Torr as well as 0.8 g of a fraction from boiling point 90 to 105/6 Torr and finally 0.5 g residue d.

Saponification number 285.7; », = 1.4592,
spcz. Weight 0.9771.

5 components can be determined by gas chromatography (175 °):

(1) 4.2% (2) 14%. (3) 33.3% (4) 27.1% (5) 21.4%

In the IR spectrum, a carbonyl band is found at 5.75 μ and a propional band at 8.4 μ. The product has a green fruity as well as a green woody smell with a NoIc of anise.

yfo

The odor of the product is similar to the odor of the propionates of Example 2, but softer and less green.

Example 9

6-ethyltricyclo (2.2, 1.0, ^2h ) -heptan-3-ol and
5-ethylidene norbornane-2- and -3-oi

100 g of a mixture of 6-ethyltricyclo (2.2.1.0 ^2h ) -hept-3-yl-acetal and 5-ethylidene norborn-2- and -3-ylacetate (Example 1). 200 g of methanol and 137 g of aqueous 45% strength potassium hydroxide solution are refluxed at 77 with stirring. 200 ml of water are then added and the methanol is distilled off at a bath temperature of 90 '. 100 ml of benzene are added. separates the lower aqueous layer and extracts it twice with 50 ml of renzene each time. The combined oily benzene extracts are washed neutral with water and the benzene is then distilled off under reduced pressure. 75 g of an alcohol mixture remain, which is vacuum distilled at 6 Torr in a 37 cm column filled with glass bodies. 70.6 g (92.5% of theory) of the desired product with a boiling point of 82 to 85 6T01T aN are obtained, also a fraction of 1.5 g with a boiling point of 73 to 87 6 Torr and 2.0 g of residue.

Shelfunus value (after acetylation) 306.7:

/ 1 = 1.4975. "

5 components can be detected by gas chromatography (150):

35

The product has a soft, green, woody and camphor-like odor. In the IR spectrum becomes an alcohol band at 3.00 μ and at 9.5 μ a secondary alcohol bandc demonstrated.

(D 11.1%. (2) 35.1%. (3) 3.0%. (4) 40.5%, (5) 10.3%.

Example 10

6-Alhyltricyelo (2.2.1,0 ² ") -heplan-3-ol and
5-ethylnorbornan-2- and -3-ol

A mixture of 86 g of ethyl tricyclo (2.2, l. () ² '') -heptan-3-ol and S-ethylidynorbornan ^ - and -3-ol (Example 9) are in the presence of 2.0 g of palladium (5 % on coal) hydrogenated in a Parr bomb at 60 and 2.7 to 3.4 atm hydrogen pressure. The absorption of hydrogen is over after 5 hours. The hydrogen taken up corresponds to 0.37 mol, the hydrogenation is 61%, which means that the 5-ethylidene norbornanols have been hydrogenated to the 5-ethylnorbornanols. The reaction product is filtered and the crude alcohol mixture at 5 Torr in a 37-em column, filled with glass bodies, vacuum deslillieri. 82.2 g (94% of theory) of the desired product with a boiling point of 80 to 827 5 Torr are obtained, as well as a fraction of 1.8 g with a boiling point of 76 to 84/5 Torr and 1.5 g of residue.

Acetylation number 302.5,

"■ ;; = 1.4825.

55 Gas chromatography (175 I can determine 4 components:

(2) 26.6%.

(3) 4S.2%,

(4) 18.2%.

The product has a green, woody and minty odor.

In the IirHR spectrum, a band at 2.9 μ is detected (Alcohol) as well as one at 9.5 μ (secondary alcohol).

Example 11

6-Aihyltricyelo <2,2.1,0 ^2l ') -heptan-3-one and
S-ethylnorbornane ^ - and -3-one

175 g of a mixture of Ethyltncyc / o (2.2J.0 ² V hepian-3-ol and S-Älhylnorbornan ^ - and -3-ol (Example 10), 155 g of sodium dichromate and 1135 ml of water are heated to 50 °. under cooling 'are added _2% sulfuric acid. it holds are added over a period of 30 minutes 326 g ¹ _2% igc sulfuric acid. the mixture is kept for a further 4 hours at 50' over a period of 30 minutes 326 g 62nd Well 100 ml of benzene are added and the layers are allowed to separate. The aqueous acidic layer is extracted twice with 100 ml of benzene each time. The oily benzene layers are combined with 50 ml of water, with 1% sodium bicarbonate solution and then again with The benzene is distilled off under reduced pressure, 156 g of a ketone mixture remaining.This crude product is vacuum distilled in a 37 cm column filled with glass bodies, giving 113.2 g (65.5% of theory) of the desired product at the boiling point 59 to 62 "4Torr as also a fraction of 1.8g with a boiling point of 53 to 100 4 torr. 13.5 g from the boiling point 83 to 98 0.5 Torr and 26.0 g residue.

Carbonyl value 391.8; / 1 = 1.4732.

5 components can be detected by gas chromatography (175):

45

(D 0.9% (2) 13.8% (3) 82.6% (4) 2. (YV _n (5) 0.7 "/,

The product has an interesting, strong, green, woody odor.

In the IR spectrum, an (arbonyl band detected.

Example 12

The mixture of 6-Alhyllricyclo (2.2, l, 0 ^:! '') -Hcpt-3-yl-acetal and 5-Ethylidennorborn-2- and -3-yl-acetate (Example 1) has a green, fruity , slightly greasy odor and can go well with pine notes, /. B. bornyl and isobornyl acetate. be mixed. 3% of the above-mentioned acetate mixture can be incorporated into the following formulation with Kiefcninote:

(icwichtleile

Bornylcelate 144

Copaiba oil 82

I-needle oil 131

, -'- ionone 7

Isobornylaciate 400

Labdanum absolute 10

Lavender Oil 41

Linalool 70

Linalyl acetal 33

Patchouli oil 8

-Isocamphylcyclohexanol 33

Vanillin. 10% in diethyl phthalate 3

Ylang Bourbon 8

Acetates (Example 1) 30

1000

By incorporating these acetates of Example 1, the original formulation is extremely high modified in an interesting way.

The acetates of Example 1 can be used in most Perfume compositions are used in amounts of 0.1 to 10%. But there are also higher concentrations. z. B. higher than 50%. possible, whereby special effects can be achieved.

Example 13

The mixture of 6-ethyltricyclo (2.2 l, O ^{2 /} ') -hept-3-yl-propionate and 5-ethylidene norborn-2- and -3-ylpropionate (Example 2) has a fresh, green, woody odor slightly fruity character. These esters mix well with hcliolropin and anisaldehyde notes. They were incorporated in the following heliotropin base in an amount of 1%:

Gcwichlslcile

Anise alchyd 10

Diethyl phthalate 500

Geraniol 20

Heliotropin 250

Xylene musk 10

Orange oil 20

Peru balm 20

Rose oil (Bulgar.) 10

Vanillin ". 150

Propionate (Example 2) 10

1000

45 By adding the propionates from Example 2

In the above formulation, the flowery character of the composition was increased and progressed. The composition this gives it a more pleasant note. The propionates can, for. B. in amounts from 0.1 to 10% added graze. In order to achieve special effects, however, higher amounts can also be used.

Example 14

The mixture of 6-Ethyltrieyelo (2.2, ^{1.0, 2l} ') -hepl-3-yl-propionate and 5-Älhylnorborn-2- and -3-ylpropionate (Example H) has a soft, woody odor with a slightly green early character and is well suited for incorporation in perfume compositions. The propionates were incorporated into the following lasmin formulation in an amount of 5%:

Hydroxycitronellal-methylanthranilal (Schiff base, 10% in diallyl phthalate)

Benzyl acetate

Gcwichisleile Gcuichlsleilc

Cananga Oil 30

p-cresylphenyl acetate

1% in diallyl phthalate iv

Hexyl cinnamaldehyde 65

Hydroxycilronellal 105

Linaiool 220

Ambrette Musk 21

Phenyl ethyl alcohol 200

isocamphylcyclohexanol 43

Undecalactone, 10% in diethyl phthalate 19

Ylang Bourbon 19th

Propionate csier (Example 8) 50

1000

By incorporating the propionates of Example 8 into the above formulation with jasmine character the head of the formulation is given a pleasantly fruity, woody character. the Propionates can normally be added to most perfume compositions in amounts of 0.1 to 10%. It can also be used in higher concentrations to achieve special effects can be used.

Example 15

The mixture of 6-Äthyllricyclo (2,2.1,0 ^{2 <1} ) -heptan-3-ol and S-Äthylidennorbornan ^ - and -3-ol (Example 9) as well as the mixture of 6-Äthyltricyclo (2.2.1, 0 ^{2 (>} ) - heptane - 3 - oil and 5 - ethylnorbornan-2- and -3-ol (Example 10) has a similar strong, green, woody odor, and these mixtures are valuable ingredients for perfume formulations especially for formulations with coumarin and amyl salicylate salts.

The above alcohols of Examples 9 and 10 were the following Fougcrcbasc in an amount of 5% added:

Weight partc

Amyl salicylate 121

Benzyl acetate 364

Bergamot Oil 242

Coumarin 121

Lavender oil 12

Linalyl acetate 12

Ambrelte Musk 24

Oak moss, 10% in diallyl phthalate. . 12th

Patchouli oil 6

Isocamphylcyclohexanol 24

Vanillin, 10% in diethyl phthalate 12

Alcohols (example 9) or alcohols

(Example K)) 50

1000

By adding the alcohols of Example 9 or 10 to the above Fougercbasc, its odor is increased, and the base receives an interesting and original woody note that matches the previously known Fragrances could not be reached. The alcohols can be perfume compositions such. B. in quantities from 0.1 to 10% can be added.

Example 16 The mixture of the ketones: 6-Ethyltricyclo (2,2,1,0 ² ") -heptan-3-one and 5-Ethylnorbornan-2- and -3-one (Example 11), has a strong, green, woody odor that goes well with carvone, coumarin and

55

Ciewichlsleile

21 22

Amylsalieykit tolerates. The ketones were accordingly by the incorporation of ketones of the two following Fougerebase in an amount of game 11 in the above Fougerebase, the odor gains 2%: "_ this base in body and strength, and the Carvonnole a ,,:., C-CW ^ UStCLc _{vv! Rd} J ₁ I _01011761111 , reinforced. Without the presence of dic-

Benivl. pi T -V- ^{5 ser} ketones, the smell is neither pleasant nor

Rpra-irn m "l iin ^slark · ^The ketones can be used in odoriferous compositions

1I carvone m ^z · ^B - ⁱⁿ mem-enes from 0.1 to K) ",, are inserted / t.

_r · "! Instead of adding the new esters, as in the

I -ivenrie oil ii Examples 12 to 14 described, but can also

I in-.lvl ·, ρ, Ι 7 ό ^ uiabc dcrjeniiien esters according to Examples 3

"" i W ^b '^ ⁷ are obtained, with the

Diethylph ^ a, .. Π ^ ISf "

! / 23 ^? ^ ^ AsS

ν., ^, ιι; Γηο / · r> ···.! ι u.i ι, -. '5 canteens from around 0.1 to K) / »KieclistoiiKomp.i-

Van ll.n 10 / "in D. ethyl phthalate 2 - - _{d Um e / jcl | ct: 1Tckle zu}

Ketones (Be.sp.el 11) _JQ _{emc] en kgnncn abcr higher McIlgcn eingcsct / I}

become, ζ. Β. 50% or even more.

Claims (1)

Formulas i a, I b and I c Patent claims: I. Bicyclo (2,2,1) - heptane and tricyclo (2,2, l, 0 ^2l ') - heptane derivatives of the general formulas la, Ib and Ic (Ia)