DE2826841A1 - ODOR CONTROL AGENTS - Google Patents

Description

DR. BERG DIPL.-ING. STAPI ⁷ DIPL.-ING. SCHWABE DR. DR. SANDMAIR

PATENT LAWYERS 9 P? R 8 £

P.O. Box 86 02 45, 8000 Munich 86

Lawyer File 29 153 June 19, 1978

MONSANTO COMPANY St. Louis, Missouri / USA

Odor control agents

Lawyer File 29 153

! »3-21-41J19A GW

809851/1039

(089) 988272 Mauerkircherstc 45 ■ 8000 Munich 80 Banks: 988273 Tetegrams: Bayerische Vereinsbank Manchen 453100 988274 BERGSTAPF PATENT Munich Hypo-Bank Munich 3890002624 983310 TELEX: 0524560 MOUNTAIN Posischeck Munich 65343-808

-r-

description

The invention relates to the treatment of intense odors, in particular means and methods for combating certain ones malodorous smell c

Some perfuming was probably done in the cavernous dwellings of the past. From these beginnings until relatively recently, perfumers used animal and natural perfume chemicals of vegetable origin. The perfumers have the natural perfume chemicals e.g. the essential oils, such as rose oil and Clove oil and animal secretions, like musk, processed to create different scents. A few years ago however, perfume researchers have developed a large number of synthetic chemicals that have the aroma properties that have been desired so far. These synthetic aroma chemicals have opened up a new field of work for perfumers, since the compounds so produced are generally chemically stable and cheaper than the natural perfume chemicals. These chemicals can be manipulated more easily than the natural perfume chemicals, since the natural perfume chemicals are usually very complex and can therefore hardly be analyzed chemically. The synthetic aroma chemicals, on the other hand, have a known one chemical structure and can therefore be treated or modified by the perfumer for specific purposes. The arrival

809851/1039

Turnaround areas often vary over a wide area. There is therefore a great need in the perfume industry for compounds which have special odor properties.

Great efforts have therefore been made in the perfume industry to provide means for combating odors which humans perceive to be malodorous. Such a variety of odors odor notes, for example, include the bathroom, kitchen, body, cigar smoke odor, etc. have been developed to combat these odors many products, such as the so-called "air fresheners" or "space deodorant ± s ⁿ show.

These products generally work with one of two masking effects. The masking fragrance is either superimposed on the intense odor, whereby a more pleasant fragrance is formed in larger quantities, or it mixes with the intense odor, whereby another, more pleasant fragrance note is formed. This masking has the disadvantage that in both cases a large amount of the fragrant fragrance must be used, which in turn leads to the formation of an intense fragrance. In addition, the intense odor to be combated is usually still noticeable with the applicable or tolerable amount of the fragrant masking agent.
>

* - 7 -

809851/1039

There are therefore desired means and methods for controlling odors which substantially eliminate the odors, without causing the disadvantages listed above.

In particular, harmful or poisonous gases can be combated with compounds that have a clear tendency to give off or have uptake of protons. Such compounds are identified as malodorous compounds in the following text. They include the notorious odor classes of the lower carboxylic acids, thiols, thiophenols, phenols, lower amines, phosphines and arsenic.

From US-PS 4009 253 it is known, for example, that 4-cyclohexyl-4-methyl-2 <-pentanone can be used to combat such malodorous compounds. (See also the US patent applications 628 855, 640 614, 751 773 and 761 750).

The compounds in the table below are described in the literature. However, it was not known that these compounds can be used for combating malodorous compounds.

809851/1039

Tabel

S-methylcyclohex-3-en-1-ylmethyl methacrylate Nordstrom, U.S. 3,536,687

(CA 74, P32769b)
3- (6'-Methylcyclohex-3'-en-1'-y1) -prop-1-en-3-yl acetate.-Kugatova et al., Zh. though. Khim. (1961)

31, 604 (CA 55.22175h)
3- (cyclohex-3'-en-1'-yl) -prop-1-en-3-yl-acetate - Kugatova et al. Zh. though. Khim. (1961) 31 ,

604 (CA 55.22175h)
1- (cyclohex-3'-en-l'-yD-propan-l-yl acetate. - Petrov et al., J. gen Chem. USSR (1952) 2J2,

591 (CA 47.2736a)
1- (cyclohex-3'-en-1'-yl) -2,2-dimethyl propan-1-yl acetate — Kugatova et al., Zh. Organ. Khim. (1967)

3 (7) , 1220 (CA 67.90430a)
2- (4 ^I -methylcyclohex-3'-en-l'-yl) -propan-2-yl acetate - Petrov et al., J. gen. Chem. USSR (1952) 22_,

591 (CA 47.2736a)
2- (4'-Methylcyclohex-3'-en-1'-yl) propan-2-yl propionate - Kogami et al., Kogyo Kagaku Zasshi

(1971) 74 (11) , 2304 (CA 76,34415y) 1- (cyclohex-3'-en-1'-yl) -ethan-1-yl-acetate - Petrov et al., J. gen. Chem. USSR (1952) 2_2, 591 (CA 2736a)

1- (cyclohex-3'-en-1'-yl) -2-methylpropan-1-yl acetate - Petrov et al., Zhj abj., K & tfn. (1957) 27 , 1795 (CA 52,4517a)

1- (Cyclohex-S'-en-l'-yl) -pentan-l-yl-acetate - Petrov et al., Zh. ofasch. Khim. (1957) 2-7, 1795

(CA 52,4517a)
1- (Cyclohex-3'-en-1'-yl) -3-methylbutan-1-yl acetate - Petrov et al., Zh. though. Khim (1957) 2T_, 1795

(CA 52,4517a)
2,6, δ-trimethylcyclohex-lren-l-ylmethyl acetate - Rudenko et al, Izvest, Ak. Nauk, SSSR, Otdel

Khim. Nauk (1962), 236
2,6,6-Trimethylcyclohex-2'-en-1'-ylmethyl-acetate- - Smit et al. , Izvest. Ak. Nauk. SSSR, Otdel Khixn.

Nauk (1959), 1848 (CA 54.8887g) and Smit et al-, Izvest. Ak. Nauk. SSSR, Otdel Khim. Nauk (1962),

470 (CA 57.1254Ie)
4- (Cyclohex-3'-en-1'-yl) -but-1-en-4-yl-acetate .-- Sopo-v et al., Zh. even though Khim. (1963) 33 (6) , 1827

(CA 59.7384e)
4- (6 '-Methylcyclohex-3' -en-1 'yl) -but-1-en-4-yl-acetate - Sopov et al., Zh. though. Khim (1963) 33 (6) ' , 1827

(CA 59.7384e)
1- (4 ', 6'-Dimethylcyclohex-3'-en-1'-yl) -butan-1-yl acetate -Sopov et al., Zh. though. Khim- (1963) 33 (4) , 1142 (CA 59,9827a) and Sopov et al-, Zh.

though. Khim. (1964) 34 (5) , 1492 (CA 61,5529d) 1- (4 · -Methylcyclohex-3'-en-1'-yl) -hexane-1'-yl-acetate - _m Sopov et al., Zh . though. Khim. (1963) 33 (4) , co 1142 (CA 59.9827a)

cn 4- (2 ', 6'-Dimethylcyclohex-3 ^l -en-l'-yi) -but-l-en-4-yl-

^ acetate Sopov et al., Zh. though. Khim. (1963)

Ca> 33 (4) , 1142 (CA 59.9827a) and Sopov et al., Zh. (O

though. Khim. (1964) 34 (5), 1492 (CA 61,5529d)

-yf-

4- (4 '-Methylcyclohex-3' -eix-1 '-yl) -but-1-en-4-yl-2 ο 2 6 O 4 I. acetate — Sopov et al., Zh. though. Khim. (1964)

34 (5) , 1492 (CA 61,5529d)
4- (2 '-ilethylcyclohex ^' -en-1 '-yl) -but-l-en-4-yl-

acetati — Sopov et al., Zh. though. Khim. (1964)

34 (5) , 1492 (CA 61,5529d)
1- (6'-Methylcyclohex-3'-en-1'-yl) »butan-1-yl acetate \ - Sopov et al., Zh. Organ. Khim. (1965) 1 (2) ,

233 (CA 62.14519g)
1- (6'-Methylcyclohex-3'-en-1'-yl) -2-methylpropan-1-ylacetate * -Sopov et al., Zh. Organ. Khim. (1965)

1 (2) , 233 (CA 62.14519g)

1- (Cyclohex-3'-en-1'-yD-hexan-1-yl acetate - Sopov et 'al., Zh. Organ. Khim. (1965) 1 (2) , 233 (CA

62.14519g)
1- (6'-Methylcyclohex-3'-en-1'-yl) -hexan-1-yl-acetate - Sopov et al., Zh. Organ. Khim. (1965) 1 (2) , 233
(CA 62.14519g)

1- (6'-Methylcyclohex-3'-en-1'-yl) -butan-1-yl-acetate -. Sopov et al., Zh. ' Organ. Khim. (1965) 1 (2) , 233
(CA 62.14519g)

1- (2, 2, 4'-trimethylcyclohex-3'-en-1'-yl) -ethan-1-yl-

acetate —Sopov, Zh. Organ. Khim. (1965) 1 (3) , 446 (CA 63.1712e)
4- (3 ', 4'-Dimethylcyclohex-3'-en-1 ¹ -yl) -but-1-en-4-yl-

co acetate · —Sopov, Zh, Organ. Khim. (1965) 1 (5) , 827 ο

co (CA 63,6885a)
oo

^ 4- (3 ', 4', Ö'-Trimethylcyclohex-S'-en-l'-yD-but-l-en-

4-yl acetate —Sopov, Zh. Orgai ... Khim. (1965) 1 (5) ,

ω 827 (CA 63.6885a).

2- (Cyclohex-3 ¹ -en-1'-yD-propan-2-yl-acetate.

Ramegouda et al., Ind. J. Chem. (1972) 10 (12), 1194

/ η /

The present invention relates to compounds and compositions which are particularly useful for combating malodorous odors can be used. The invention also relates to methods for combating malodorous odors or the use of the above compounds and agents.

The compounds surprisingly useful in controlling malodorous smells are provided by the following Formulas marked:

(1)

(2) i

η is an integer from 1 to 4,

A, B and C each independently represent hydrogen, lower alkyl with 1 to 5 carbon atoms or lower alkenyl with 3 to 5 carbon atoms, provided that the sum of the carbon atoms in A, B and C is not greater than 7,

809851/1039

- 12 -

-χ-

1 2

R and R each independently represent hydrogen

or lower alkyl or alkenyl with 1 to 5 carbon atoms, R stands for hydrogen or lower alkyl or alkenyl with up to 6 carbon atoms, provided that the sum of the larger numbers of carbon atoms
is greater than 10.

12 3 numbers of carbon atoms in either R or R plus R not

The term "control" as used herein refers to human odor perception and / or the reduction of Intensity of malodorous smells in relation to human odor perception. The word "combat" is not considered Restriction to a particular mechanism by which such odor improvements are achieved.

The compounds of the general formula I according to the invention can be prepared as can be seen from the following scheme will:

+ C

Il

(D.

(where X is hydrogen, alkyl or alkenyl)

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809851/1039

(where X is hydrogen)

R ² MgCl

(where X is alkyl or alkenyl (R))

Esterification

or
Acylation.

(IV)

12 4

In the above equations, A, B, C, R, R, and R have the above given meanings. X has the meaning given in the respective equations.

As indicated in equation (I), a substituted or unsubstituted 1,3-diene with a substituted or unsubstistiuierten Ot, ß-Unsaturated aldehyde or ketone implemented, where the corresponding aldehydes or ketones are formed

809851/1039

- 14 -

be det. As given in equation (Ha), that becomes corresponding aldehyde or ketone reacted with a suitable Grignard compound, the corresponding secondary alcohol is formed. However, as shown in equation (Hb), the aldehyde or the ketone can also be reacted with a metal hydride be, with the corresponding cyclohex-3-en-l-ylmethanol is formed. If desired, however, as shown in equation (III), the aldehyde or the ketone can also be used a suitable Grignard compound, the corresponding tertiary alcohol being formed. the equation (IV) shows the formation of the esters of the invention, e.g., by esterification of the primary and secondary alcohols and by acylation of the tertiary alcohols.

The compounds of the general formula (2) according to the invention can be prepared according to the following reaction scheme:

T L

-CN

OH

CN

'CHO

HCN

Dehydration ^

reduction

809854/1039

A.

t — i—

Metal ^^
Hydride ^ B l

Ll

(VII) CHO

(VIII)

OH

H H

R ¹ MgCl

XHO

R ¹ HgCl

+ Hydrolysis

R ² MsCl

Esterification

or acylation -

R R

(XI)

.0 (XII)

12 3
A, B, C, R, R and R have the meanings given above.

As shown in equation (V), a substituted
or unsubstituted cycloalkanone reacted with HCN, where
the corresponding cyanohydrin is formed, which is then dehydrated to the corresponding δ, ß-unsaturated nitrile (equation (VI)>. Equation (VII) shows the reduction of the corresponding cC, ß-unsaturated cycloalkenyl carbaldehydes. In equations (VIII) and ( IX) shows how the aldehyde is reacted with a metal hydride or a Grignard compound to form the corresponding primary or secondary alcohols. Equation (X) shows how that

809851/1039

- 16 -

4 *
-yf-

Cyanohydrin is reduced to the corresponding ketone by reaction with a suitable Grignard compound and hydrolysis. The ketone prepared according to equation (X) is with a reacted with another Grignard compound, whereby a tertiary alcohol is formed (see equation (XI)). Like the equation (IV) Equation (XII) shows the esterification or acylation of the compounds for the preparation of the esters according to the invention.

The compounds of the invention are useful for effective control of malodorous smells can be used, the compounds in small amounts and in many different Media can be used. The compounds of the invention are preferably used in indoor air fresheners or room deodorants in the form of aerosols (sprays, etc.), liquids (wick type), solids (based on wax in Pomander, in plastic bodies, etc.), powders (scented sachets, dry spray) and gels (solid gel pens) are used. Other exemplary areas of application for the compounds according to the invention are clothing deodorants which are used in the washing machine used, e.g. in detergents, washing powders, washing liquids, Brighteners or fabric softeners, applications in toilet cleaners, toilet aerosols, sprays or in the Clothes storage; in bathroom accessories, e.g. paper towels, Bathroom towels, sanitary napkins, hand towels, disposable clothing. Disposable napkins, in deodorants for Napkin holders; in cleaning agents, e.g. disinfectants and cleaning agents for toilet bowls? in

809851/1039

- 17 -

Af

cosmetic products, e.g. antiperspirants and arm deodorants, in common body deodorants in the form of powders, aerosols, liquids or solids, or in Hair treatment products, e.g. hair sprays, hair treatment tools, hair rinsing agents !!, hair dyes and tints, permanent waving agents, depilatories, hair setting agents, Hair shine agents, e.g. pomades, creams, lotions, etc., medicinal hair treatment agents containing S-selenium sulfide, Coal tar products, salicylates, etc., or in shampoos or in foot treatment products, e.g. foot powders, liquids or Foot waters, after-shaves products and body lotions or in soaps and synthetic detergents, e.g. in pens, Liquids, foam products or powders; in odor control, e.g. for use in manufacturing processes, e.g. in the textile aftertreatment industry and in the printing industry (inks and paper); at the odorber: fighting, e.g. in processes for the production of paper pulp, in slaughterhouses and in meat processing, for the treatment of waste water, in garbage chutes, in products for Combating odors in the aftertreatment of textiles, in rubber aftertreatment products, in agents for treating the air in passenger compartments of cars, etc .; in agricultural Products and in products for the treatment of animals, e.g. dogs and chickens and pets and pet treatment products, e.g. deodorants, shampoos or cleaning agents or in animal waste products; in large quantities in closed room air systems, e.g. auditoriums, subways and transport systems.

809851/1039

- 18 -

The amount of the compound used according to the invention is generally independent of the particular odor nuisance. It has been found that the concentration of the odor nuisance compounds in the air is the most effective Do not affect the amount of compound used. It is only necessary to ensure that an effective Amount is used to combat the malodorous compounds. The amount of the to be used according to the invention Compound, however, depends on the medium in which it is used, the temperature, the humidity, the volume of air and air circulation. The compounds of the invention are generally effective when in the air (containing the malodorous compounds) in an amount of at least 0.01 mg /. cbm of the air to be treated is present. Some of the compounds of the invention are more effective than the others because of their chemical structure. Any concentration or below the lower limit given above is generally effective. However, it is for practical reasons unnecessary to use more than about 1.0 to 2.0 mg / cbra air.

Of the compounds according to the invention, those which contain a cyclohexene ring in the molecule are particularly preferred, for example 3-cyclohexenylmethylformate and 2- (cyclohex-3 ¹ -en-1'-yl) propan-2-ylacetate.

Further exemplary compounds according to the invention are summarized in the following table:

809851/1039

Z *

2- (Cyclopent-1'-en-1'-yl) -propan-2-y1-acetate-2- (Cyclopent-1 ¹ -en-1 ¹ -yl) -propan-2-y1-n-propionate 2 - (Cyclopent-1'-en-1'-yl) - propan-2-yl-n-butyrate 2- (Cyclohept-1'-en-1'-yl) - propan-2-y1-acetate 2- ( Cyclohept-1'-en-1'-yl) -propan-2-yl-n-propionate 2- (Cyclohept-1'-en-1'-yl) -propan-2-y1-n-butyrate.

2- (Cyclooct-1'-en-1'-yl) - propan-2-yl-acetate 2- (Cyclooct-1'-en-1'-yl) - propan-2-y1-n-propionate 2- (cyclooct-1'-en-1'-yl) -propan-2-y1-n-butyrate 1- (cyclopent-1'-en-1 ^1-yl) -ethane-l-yl acetate; 1- (Cyclopent-1'-en-1'-yl) -ethan-1-y1-n-propionate 1- (Cyclopent-1'-en-1'-yl) -ethan-1-y1-n-butyrate 1- (Cyclohept-1'-en-1'-yl) - athan-1-y1- ^ c ~ tat.

1- (Cyclohept-1'-en-1'-yi) -ethan-1-yl- n.-p'-opj.onat 1- (Cyclohept-1'-en-1'-yl) -ethan-1-y1-n-butyrate.

1- (Cyclooct-1'-en-1 '-yl) -ecian-i-yl acetate 1- (Cyclooct-1'-en-1 ¹ -yD-echan-1-yl-n-propxonate 1- (Cyclooct- ^{1'-en-1 1} -yl) -athan-1-y1-n-butyrax:

4, S-Dimethylcyclohex-i-en-vlmethane-1-y1-acetate.

4, e-Dimethylcyclohex-3-en-ylmethan-1-yl-n-propionate 4,6-Diinethylcyclohex-3-en-ylmethan-l-yl-n-butyraT:

2, S-Dimethylcyclohex-S-en-ylmethan-1-yl-acetate 2,5-0imethylcyclohex-3-en-ylmethan-1-y1-n-propionate.

2,5-dimethylcyclohex-3-en-ylmethan-1-y1-n-butyrate 3,5,5-trimethylcyclohex-3-en-ylmethan-1-y1-aceta-3,5, b-Trxynethylcyclohex-3-en-ylme than-1-yl-n-propionate SjSiS-trimethylcyclohe-x-S-en-ylmethan-1-yl-n-butyrate

809851/1039

2,2,4-trimethylcyclohex-3-en-yimethan-1-yl acetate 2,2,4-trimethylcyclohex-3-en-yimethan-1-yl-n-propionate 2,2, ^ - trimethylcyclohex-S-en-ylmethan-1-yl-n-butyrate 2,6,6-Trimethylcyclohex-3-en-ylmethan-1-yl-acetate 2,6,6-trimethylcyclohex-3-en-ylmethan-1-yl-n-propionate 2,6,6-Trimethylcyclohex-3-en-yimethan-1-yl-n-butyrate 2,6,6-Trimethylcyclohex-1-en-ylmethan-1-yl-acetate 2,6,6-trimethylcyclohex-1-en-ylmethan-1-yl-n-propionate. 2,6,6-Trimethylcyclohex-1-en-yimethan-1-yl-n-butyrate 2,2,4-Trimethylcyclohex-1-en-ylmethan-1-yl-acetate 2,2,4-trimethylcyclohex-1-en-yimethan-1-yl-n-propionate 2,2,4-Trimethylcyclohex-1-en-ylmethan-1-yl-n-butyrate J. 2-methylcyclohex-3-en-ylmethan-1-yl-acetate 2-methylcyclohex-3-en-ylmethan-1-yl-n-propionate-2-methylcyclohex-3-en-yimethan-1-yl-n-butyrate 4-methylcyclohex-3-en-ylmethan-1-yl-acetate 4-methylcyclohex-3-en-yimethan-1-yl-n-propionate 4-methylcyclohex-3-en-yimethan-1-yl-n-butyrate 4-methylcyclohex-1-en-yimethan-1-yl acetate. 4-methylcyclohex-1-en-yimethan-1-yl-n-propionate 4-methylcyclohex-1-en-ylmethan-1-yl-n-butyrate-5-methylcyclohex-3-en-yimethan-1-yl acetate 5-methylcyclohex-3-en-yimethan-1-yl-n-propionate 5-methylcyclohex-3ren-yimethan-1-yl-n-butyrate 6-methylcyclohex-3-en-ylmethan-1-yl-acetate 6-methylcyclohex-3-en-yimethan-1-yl-n-propionate 6-methylcyclohex-3-en-yimethan-1-yl-n-butyrate 4-Ethylcyclohex-1-en-ylmethan-1-yl-acetate

4-Ethylcyclohex-1-en-ylmethan.-1-yl-n-propionate ·. 809851/1039

4-Ethylcyclohex-1-en-ylmethan-1-yl-n-butyrate. S-ethylcyclohex-S-en-ylmethan-l-yl-acetate-S-ethylcyclohex-S-en-ylmethan-1-y1-n-propionate S-ethylcyclohex-3-en-ylethan-1-yl-n- butyrate 4-ethylcyclohex-3-en-ylmethan-1-y1-acetate-4-ethylcyclohex-3-en-ylmethan-l-yl-n-propionate 4-ethylcyclohex-3-en-ylmethan-l-yl-n- butyrate 4-isopropylcyclohex-l-en-ylmethan-l-yl-acetate 4-isopropylcyclohex-1-en-ylmethan-l-yl-n-propionate 4-isopropylcyclohex-1-en-ylmethan-l-yl-n- butyrate 4-isopropenylcyclohex-1-en-ylmethan-l-yl-acetate 4-isopropenylcyclohex-l-en-ylmethan-l-yl-n-propionate 4-isopropenylcyclohex-1-en-ylmethan-l-yl-n-butyrate 4-Isopropylcyclohex-3-en-ylmethan-1-yl-acetate 4-Isopropylcyclohex-3-en-ylmethan-1-yl-n-propionate 4-Isopropylcyclohex-3-en-ylmethan-1-yl-n-butyrate 4 -tert.3utylcyclohex-1-en-y! methan-1-yl acetate 4-tert-butylcyclohex-1-en-ylmethan-1-yl-n-propionate 4-tert.-butylcyclohex-1-en-ylmethane-1 -yl-n-butyrate 4-tert-butylcyclohex-3-en-ylmethan-1-yl-acetate. 4-tert-butylcyclohex-3-en-ylmethan-1-y1-n-propionate 4-tert-butylcyclohex-3-en-ylmethan-l-yl-n-butyrate 1- (cyclohex-1'-en-1 ' -yl) "ethan-1-yl-acetate 1- (Cyclohex-1 ¹ -en-1 ¹ -yl) -ethan-1-yl-n-propionate 1- (Cyclohex-1'-en-1'-yl ) -ethan-1-yl-n-butyrate 1- (cyclohex-3'-en-1'-yl) - ethan-1-yl-acetate 1- (cyclohex-3'-en-1'-yl) -ethan-1-yl-n-propionate 1- (cyclohex-3'-en-1'-vl) »ethan-1-yl-n-butyrate

8098 ^ 5.1 / 1039

1- (Cyclohex-3'-en-1'-yl) -propan-1-yl-acetate. 1- (Cyclohex-3'-en-1'-yl) -propan-1-yl-n-propionate 1- (Cyclohex-3'-en-1'-yl) -propan-1-yl-n-butyrate 2- (Cyclohex-3'-en-1'-yl) -propan-2-yl-acetate 2- (Cyclohex-3'-en-1'-yl) -propan-2-yl-n-propionate. 2- (Cyclohex-3'-en-1'-yl) -propan-2-yl-n-butyrate 1- (Cyclohex-3'-en-1'-yl) butan-1-yl acetate 1- (Cyclohex-3'-en-1'-yl) -butan-1-yl-n-propionate 1- (Cyclohex-3'-en-1'-yl) -butan-1-yl-n-butyrate · 1 - (Cyclohex-3'-en-1'-yl) -2-methylpropan-1-yl-acetate 1- (Cyclohex-3'-en-1'-yl) -2-methylpropan-1-yl-n- propionate · 1- (cyclohex-3 ¹ -en-1'-yl) -2-methylpropan-1-yl-n-butyrate. 2- (Cyclohex-3'-en-1'-yl) -butan-2-yl-acetate 2- (Cyclohex-3'-en-1'-yl) -butan-2-yl-n-propionate 2- (Cyclohex-3'-en-1'-.yl) -butan-2-yl-n-butyrate 1- (Cyclohex-3'-en-1'-yl) -pentan-l-yl-acetate 1- ( Cyclohex-3'-en-1'-yl) -pentan-l-yl-n-propionab 1- (Cyclohex-3'-en-1'-yl) -pentan-1-yl-n-butyrate 1- ( Cyclohex-3'-en-1'-yl) -2-methyl-butan-1-yl-acetate.

1- (Cyclohex-3'-en-1'-yl) -2-methylbutan-1-yl-n-propionate 1- (Cyclohex-3'-en-1'-yl) -2-methylbutan-1-yl-n-butyrate 1- (Cyclohex-3 · -en-1'-yl) -3-methylbutan-1-yl acetate 1- (Cyclohex-3'-en-1'-yl) -3-methylbutan-1-yl-n-propionate 1- (Cyclohex-3'-en-1'-yl) -3-methylbutan-l-yl-n-butyrate:

3- (Cyclohex-3'-en-1'-yl) -l-propen-3-yl-acetate 3- (Cyclohex-3'-en-1'-yl) -l-propen-3-yl-n Propionate 3- (cyclohex-3 ¹ -en-1 ¹ -yl) -l-propen-3-yl-n-butyrate 4- (cyclohex-3'-en-1'-yl) -l-buten-4 -yl acetate.

8098 5 1/1039

If

4- (Cyclohex-3'-en-1'-yl) -l-buten-4-yl-n-propionate 4- (Cyclohex-3'-en-1'-yl) -l-buten-4-yl-n-butyrate 4- (Cyclohex-3'-en-l'-yl) -but-2-en-4-yl-acetate 4- (Cyclohex-3'-en-1'-yl) -but-2-en-4-yl-n-propionate 4- (Cyclohex-3'-en-1'-yl) -but-2-en-4-yl-n-butyrate 4- (Cyclohex-3'-en-1'-yl) -3-methylbut-1-en-4-yl acetate 4- (Cyclohex-3'-en-1'-yl) -3-methylbut-1-en-4-yl-n-

propionate
4- (Cyclohex-3'-en-1'-yl) -S-methylbut-1-en-1'-yl-n-butyrate

5- (Cyclohex-3'-en-1'-yl) -pent-2-en-S-yl-acetate. 5- (Cyclohex-3'-en-1'-yl) -pent-2-en-5-yl-n-propionate 5- (Cyclohex-3'-en-l'-yl) -pent = 2-en-5-yl-n-butyrate 1- (2'-Methylcyclohex-3'-en-1'-yl) -ethan-1-yl-acetate 1- (2'-Methylcyclohex-3'-en-1'-yl) -ethan-1-yl-n-propionate ' 1- (2'-Methylcyclohex-3'-en-1'-yl) -ethan-1-yl-n-butyrate 1- (4'-Methylcyclohex-3'-en-1'-yl) -ethan-1-yl-acetate 1- (4'-Methylcyclohex-3'-en-1'-yl) -ethan-1-yl-n-propionate 1- (4'-Methylcyclohex-3'-en-1'-yD-ethan-1-yl-n-butyrate 1- (6'-Methylcyclohex-3'-en-1'-yl) -ethan-1-yl-ecetate 1- (6'-Methylcyclohex-3'-en-1'-yl) -ethan-1-yl-n-propionate.

1- (6'-Methylcyclohex-3'-en-1'-yl) -ethan-1-yl-n-butyrate 1- (2 ', 5'-Dimethylcyclohex-3'-en-1'-yl) -ethan-1-yl -!

acetate
1- (2 ', 5'-Dimethylcyclohex-3'-en-1'-yl) -ethan-1-yl-> n-propionate

! 1- (2 ¹ ^ ¹ -Dime thy lcyclohex-3'-en-1'-yl) - ethan-1-yl- j

n-butyrate |

809851/1039

1- (4 ', e'-Dimethylcycl'ohex-3'-en-1'-y I) -ethan-1-yl-

acetate
1- (4 '/ 6'-Dimethylcyclohex-3'-en-1'-yl) -ethan-1-yl-

n-propionate,

1- (4 ', β'-Dimethylcyclohex-S'-en-l'-yl) -ethan-1-yl-j

n-butyrate;

1- (3 ', 5 ·, 5'-trimethylcyclohex-3 · -en-1 · -yl) -ethan-1-yl-

acetate i

ί l- (3 ', 5', 5'-trimethylcyclohex-3'-en-1'-yl) -ethan-l-yl-:

n-propionate;

1- (3 ', 5', 5'-trimethylcyclohex-3'-en-1'-yl) -ethan-1-yl-

n-butyrate. :

1- (2 ', 6', 6'-trimethylcyclohex-3'-en-1'-yl) -athan-1-yl-

acetate.
1- (2 ', 6 ·, 6'-Trimethylcyclohex-3'-en-l'-yl) -ethan-1-yl · "

n-propionate
1- (2 ', 6' , 6'-trimethylcyclohex-3'-en-1-yl) -ethan-1-yl-

n-butyrate
1- (2 ', 6', 6'-trimethylcyclohex-l'-en-1'-yl) -ethan-1-yl-

acetate
1- (2 ', 6', 6'-trimethylcyclohex-l'-en-1'-yl) -ethan-1-yl-

n-propionate.
1- (2 ·, 6 ', 6'-trimethylcyclohex-l'-en-1'-yl) -ethan-1-yl-

n-butyrate
1- (4 ·, 6 ', 6'-trimethylcyclohex-1'-en-1'-yl) -ethan-1-yl acetate

809851/1039

1- (4 ·, 6 ', 6'-trimethylcyclohex-l'-en-1'-yl) -ethan-1-yl -

n-propionate ~ "

1- (4 ', 6', 6'-Trimethylcyclohex-1'-en-1'-yl) - ethan-1-yl n -butyrate

l- (2 ', 4' ^ '- trimethylcyclohex-l'-en-1'-yl) -ethan-1-yl-',

acetate
1- (2 ', 4', 4'-Trimethylcyclohex-l ¹ -en-1'-yl) -ethan-1-yl * \

n-propionate
1- (2 ', 4', 4'-Trimethylcyclohex-l ¹ -en-1 ¹ -yl) -ethan-1-yln-butyrate

1- (4'-Ethylcyclohex-3'-en-1'-yl) -ethan-1-yl-acetate! 1- (4'-Sthylcyclohex-3'-en-1'-yl) - ethan-1-yl-n-propionate j 1- (4'-Sthylcyclohex-3'-en-1'-yl) -ethane 1-yl-n-butyrate 1- (4'-ethylcyclohex-l'-en-1'-yl) -ethan-1-yl-acetate, 1- (4'-ethylcyclohex-l'-en-1 '- yl) -ethan-1-yl-n-propionate '1- (4'-Ethylcyclohex-l ¹ -en-1'-yl) -ethan-1-yl-n-butyrate 1- (4'-Isopropylcyclohex- l'-en-1'-yl) -ethan-1-yl-

acetate j
1- (4'-Isopropylcyclohex-l'-en-1'-yl) -ethan-1-yl-

n-propionate.
1- (4'-Isopropylcyclohex-l'-en-1'-yl) -ethan-1-yl -

n-butyrate-1- (4'-Isopropylcyclohex-3'-en-1'-yl) -ethan-1-yl-

acetate,
1- (4'-Isopropylcyclohex-3'-en-1'-yl) -ethan-1-yl-

n-propionate
1- (4'-Isopropylcyclohex-3'-en-1'-yl) -ethan-1-yln-butyrate

809851/1 039

1- (4'-tert-Butylcyclohex-1'-en-1'-yl) - ethan-1-yl -

acetate
1- (4'-tert-Butylcyclohex-1'-en-1'-y1) -ethan-1-yl-

n-propionate
1- (4 · tert-Butylcyclohex-1 · -en-1 ' -yl) -ethan-1-yl -j

n-butyrate
1- (2 · -Methylcyclohex-3'-en-1 · -y1) - propan-1-yl - j

acetate. \

n-propionate!

-3 · -en-1-yU "propan-1-yl - j

1- (2'-methylcyclohex

n-butyrate
2- (2 ■ -Methylcyclohex-3 ■ -en-1 -yl) -propan-2-yl -

acetate i

ι T _n ^ v-en-l'-vl) -Propan-2-yl-j 2- (2'-methylcyclohex-3 en

n-propionate

2- (2'-methylcyc
n-butyrate

-, 2 ■ -Methylcydchex- 3 ■ -en-1 '-Yl) -bntan-1-yl acetate

χ. (2 -Methylcyclohex-3-en-l ■ -yll-butan-1-yl -

n-propionate
! - (2 ■ -Methylcyclohex-3 · -en-1 -yl) -butan-1-yl-

n-butyrate

809851/1039

The invention is illustrated in more detail by the following examples. However, the invention is not based on the subject matter limited examples. The term "mg / m" refers to the weight of the material in milligrams in one cubic meter Air.

example 1

3-cyclohexenyl methyl formate

A mixture of 33 _f 6g (0.3 mol) 3-cyclohexenemethanol and 46.0 g (1 mol) 97% formic acid was for 1 hour on

Heated to reflux. After cooling to room temperature the reaction mixture was poured in egg ^S water and extracted with ether, the organic material. The ether extract was washed with water, sodium bicarbonate, water and finally with a saline solution and then dried over a molecular sieve (A4) overnight. The drying agent was filtered off, the residue was washed with ether and the washing solution was combined with the filtrate. After the ether had been distilled off, 38.2 g (yield 90.8%) of the raw material were obtained, which according to GLC was 94.2% pure. The product was purified by distillation over a short Vigreux column. The 3-cyclohexenyl methyl formate was obtained as a colorless, light liquid at a boiling point of 84 ° C./18 mm Hg.

Yield 35.5 g (84.9%), purity 96.1%, n ^ ⁵ 1.4628.

The impurities consist of unreacted alcohol.

- 28 -

809851/1039

Fragrance note: Strong green, fruity chemical.

Example 2

3-cyclohexenyl methyl acetate

A mixture of 33.6 g »(0.3 moles) of 3-cyclohexenemethanol and 34.0 g (0.33 moles) of acetic acid was added to 100 mg of p-toluenesulfonic acid and the mixture was allowed to stand at room temperature for 20 hours. Then 2 ml of water was added and after 1 hour, after 1 g of sodium acetate was added, the mixture was poured into 300 ml of water. The organic phase was separated off. The aqueous phase was extracted twice with 50 ml of ether and the combined organic phase and the phase from the organic phase and the extracts were washed vigorously with water, sodium bicarbonate solution, water and brine and then dried over a molecular sieve (A4) overnight. Working up according to the method given in Example 1 gave 44.1 g of the crude product (yield 95.3%) with nl 1.4574 in a purity of 93.2% (determined by GLC). The low-boiling impurities were removed by distillation through a short Vigreux column. It was the 3-Cyclohexenylmethy1-acetate as a colorless light liquid with a boiling point of 96 ⁰ C /! ₈ ^ _Hg obtained.

Yield 40.3 g (87.1%), n ^ ⁵ 1.4576, purity: 100% (determined by GLC).
Fragrance note: Strong green, fruity, citrus-like.

809851/1039 - 29 -

-χ-

Example 3

3-cyclohexenyl methyl propionate

A mixture of 33.6 g (0.3 moles) of 3-cyclohexenemethanol and 44.3 g (0.33 moles) of propionic anhydride became 100 mg of p-toluenesulfonic acid and the solution was then left to stand at room temperature overnight. When working up according to the In the method described in Example 2, 51.2 g (yield approx. 100%) of the crude product in a purity of 99%,

n _n 1.4545 obtained, the product containing traces of the anhydride used. The product was purified by dispersion over a Vigreux column. After separating a forerun at a boiling point of 84 to 108 ° C / 18 mm Hg,

n _n 1.4312 3-Cyclohexenylmethylpropionat was obtained as a colorless, fragrant, light liquid with a boiling point of 10.8 to 110 ° C./18 mm Hg.

Yield: 43.2 g (85.6%), purity: 100% (determined by GLC), n ^ ⁵ 1.4566.

Fragrance note: green, flowery, rose-like, styrox-like.

Example 4

3-cyclohexenylmethyl isobutyrate

A mixture of 28.0 g (0.25 moles) of 3-cyclohexenemethanol and 39.6 g of isobutyric anhydride (0.25 moles) was added to 100 mg of p-toluenesulfonic acid and the mixture at night Let stand room temperature. Using the procedure described in Example 2, 42.6 g (yield 98.7%)

809851/1039 -3O-

25th
of the crude product with n _D 1.4540 and a purity of 98.73% (determined by means of GLC). The product was distilled through a Vigreux column. 3-Cyclohexenylmethyl isobutyrate was obtained as a colorless, fragrant, light liquid with a boiling point of 102 ° C./9.5 mm Hg. Yield: 39.2 g (86.0%), purity: 99.7% (determined by GLC), n ^ ⁵ 1.4540
Fragrance note: flowery, spicy, balsamic, delicate cinnamon-like.

Example 5

3-cyclohexenylmethyl butyrate

To a mixture of 28.0 g (0.25 mol) of 3-cyclohexenemethanol and 39.6 g (0.25 mol) of n-butyric anhydride was added 100 mg of p-toluenesulfonic acid and the mixture was allowed to react. When the method described in Example 2 was used for work-up, 41.3 g (90.6%) of the crude product with η 1.4565 in a purity of 96.4% (determined by means of GLC) were obtained. This product was distilled over a short Vigreux column. There were 4.1 g of the low-boiling product at a boiling point of up to 108 C / 9.5 mm Hg (n ^ ⁵ 1.4544) and 34.4 g (75.5%) of the main product at a boiling point of lo8 ° C / 9.5 mm Hg (η _β 1.4570). The main product consists of 3-cyclohexenylmethylbutyrate, which is obtained as a colorless, floral-scented, greasy-smelling liquid with a purity of 98.6% (determined by GLC).

809851/1 039

- 31 -

Example 6

2- (Cyclohex-3'-en-1'-yl) -2-propyl acetate 5.7 g (0.04 moles) of dimethylcyclohex-S'-enylcarbinol were mixed with 5 g of acetic anhydride, then 0.1 g of 85% ige phosphoric acid was added and the mixture was left to stand at room temperature for 48 hours. The reaction mixture was then poured into ice water and the organic phase was isolated as indicated in Example 2. The crude product / the 2- (cyclohex-3'-en-l-yl) -2-propyl acetate, which is obtained as a yellow liquid, was distilled. 5.3 g (72% yield) of a colorless product were obtained at a boiling point of 75 ° ^{C./3.5 mm Hg, n ^ 5} 1.4630 in a purity of 99% (determined by GLC).
Fragrance notes: lavender, lavandin, bergamot, spicy.

Example 7

The following malodorous concentrates were made;

Bath ζ always odor concentrate

Components parts by weight

Skatole 0.91

β-thionaphthol O.91

95% aqueous solution of thioglycolic acid 21.18

n-caproic acid 6, oo

p-cresyl isovalerate 2.18

N-methylmorpholine 6, oo

Dipropylene glycol 62.82

809851/1039 -32-

There were aerosol cans with the above malodorous substances produced in the following concentrations:

Bath ζ ever odor aeroso1

Component parts by weight

Bathroom odor concentrate 0.1

Dipropyl Glycol - 4.9 Propellant

a) Trichloromonofluoromethane 47.5

b) dichlorodifluoromethane 47.5

To combat the malodorous odor, a spicy was used as an example of the compounds according to the invention smelling scented water (Spice for Cologne) examined. The spicy smelling scented water contained the following ingredients:

Components parts by weight

Lavandinabrialis oil 60

Amylcinnamic aldehyde 20

Amyl salicylate 150

Benzyl acetate 30

Linalool 30

Cedarwood Oil 10

Geraniol 130

Isopulegol 6O

Methyl anthranilate (10% by weight solution in ₂

Dipropyl glycol)

- 33 -

809851/1039

28268Α1

Musk xylene 60

Coumarin 50

Phenylethyl acetate 30

Terpinylacetate 100

Cinnamon leaf oil 40

Petitgrain oil SA 130

Phenylacetaldehyde dimethyl acetate 15

Cinnamon alcohol 5

1000

Aerosol containers were made that have the above fragrance composition and the compounds according to the invention to be tested for combating odor The mixtures were composed as follows:

Ingredients percentages by weight

spicy scented water ("Spice for Cologne") 0.45

test compound according to the invention 0.05 propellant

a) Trichloromonofluoromethane 49.75

b) dichlorofluoromethane 49.75

100.00

A test room has been prepared that is 3.33 3.64 χ 2.42 m was large and had a volume of 29.9 cbm. The test room was equipped with an entrance door and an exit fan. The output fan capacity was 14.3 cbm / min.

809851/1039 -34-

in the room, the fan was between the switched on for individual attempts. In addition, before using the test room for the next experiment, one Odor check carried out to determine whether there were any residual odorous substances in the test room.

After the test room had been sufficiently evacuated, the bathroom odor produced above was sprayed into the room for 5 seconds in the form of the aerosol. After a time of 10 to 15 seconds, the fragrant aerosol composition was sprayed for a period of 5 seconds (the spray time of 5 seconds corresponds to the mean time that an aerosol is usually sprayed in the household). 1 minute later, two people entered the test room prepared in this way to check the odor and recorded their observations. One person had experience in the field of perfume and odor development and the other person had no such experience, but was familiar with fragrances of a general nature. All tests were carried out in such a way that none of the test subjects was informed of the type of materials tested. On the basis of the flow rate of the aerosol can valve, the approximate amount of aerosol containing the odor control agent and sprayed in the test room was determined (267 mg / m). which was sprayed in the test room was about 260 mg / m.

809851/1039

- 35 -

The compounds were converted into the Spicy scented water aerosol ("Spice for Cologne") incorporated. The compounds according to the invention were under Application of the test methods described above for their effectiveness in combating bathroom odor. The results are summarized in Table 1 below.

Table 1 Ingredients effectiveness ⁴ "

3-Cyclohexenylmethylformate υ

3-cyclohexenyl methyl acetate U

3-cyclohexenyl methyl propionate V

3-cyclohexenylmethyl isobutyrate U

3-Cyclohexenylmethylbutyrat ü

2- (Cyclohex-3'-en-1'-yl) -2-propyl acetate ü *

Effectiveness of the compound in combating odor according to the following classification:
U * "Extraordinary" - fresh air effect, making one

extremely light fragrance or without any fragrance residue. U "Excellent" - fresh air effect and lighter and more pleasant Background pressure.

V "Very good" - no fresh air effect but complete elimination of bad smells, various but none high background fragrance residues.

809851/1039 - 36 -

W "Good" - only traces of odor, with varying quality and residue, remaining background odor, the however, is acceptably pleasant and not too strict.

X "Impeccable" - the original odor is clearly perceptible, but with a low intensity, background odor that remains, which is however still acceptable.

Y "Weak" - the original smell is somewhat in intensity reduced, but still dominating, the generally remaining background fragrance is up to unpleasant

unacceptable.
Z "No effectiveness".

These results are particularly surprising because the test subjects found that when using the spicy Fragrance water composition aerosols without the compounds according to the invention the malodorous smells were not removed.

Even if the present invention has been explained on the basis of individual special exemplary embodiments, it is not limited to these embodiments.

809851/1039

Claims (12)

DR. BERG DIPL.-IMG. STAPF DIPL.-ING. SCHWABE DR. DR. SANDMAIR PATENTANWÄLTE Postfach 860245, 8000 Munich 86 Attorney files 29 153 patent claims 1. Means of odor control, thereby characterized in that it contains an odor control effective amount of at least one compound of the following Formulas R R (D (2) η is an integer from 1 to 4, A, B and C each independently represent hydrogen, Lower alkyl having 1 to 5 carbon atoms or lower alkenyl having 3 to 5 carbon atoms, provided that the The sum of the carbon atoms in A, B and C is not greater than 7, 809851/1039 (089) 988272 Mauerkircherstr. 45 ■ 8000 Munich 80 Banks: 988273 Telegrams: Bayerische Vereinsbank Munich 453100 988274 BERGSTAPF PATENT Munich Hypo-Bank Munich 3890002624 983310 TELEX: 0524560 MOUNTAIN Postal check Munich 65343-808 ORIGINAL INSPECTED 1 2 R and R each independently represent hydrogen or lower alkyl or alkenyl with 1 to 5 carbon atoms,
R is hydrogen or lower alkyl or alkenyl of up to 6 carbon atoms, provided that the 1 2 Sum of the carbon atoms in either R or R plus R is not greater than 10,
contains. 2. Composition according to claim 1, characterized in that the odor-controlling compound i _m is present in an amount sufficient to at least about 0.01 mg / m for the supply air containing the geruchsbelastxgenden substances. 3. Composition according to claim 1, characterized in that it is in the form of an indoor air freshener. 4. Composition according to claim 3, characterized in that it is used in the form of an aerosol. 5. A method for treating odors and reducing the intense odor note, characterized in that one the air containing the odor nuisance substances with an odor effective amount of a compound of the following formulas 8098 5 1/1039 R a or 28268 ^ 1 (i) 12) η is an integer from 1 to 4, A, B and C each independently represent hydrogen, lower alkyl having 1 to 5 carbon atoms or lower alkenyl with 3 to 5 carbon atoms, provided that the sum of the carbon atoms in A, B and C is not greater than 7, 2 R and R each independently represent hydrogen or lower alkyl or alkenyl with 1 to 5 carbon atoms,
R represents hydrogen or lower alkyl or alkenyl with up to 6 carbon atoms, provided that the sum of the 12 3 carbon atoms in each R or R plus R not larger than 10 is
treated. 6. The method according to claim 5, characterized in that the odor controlling compound is present in an amount that sufficient to reduce at least 0.01 mg / m for the odor nuisance 809851/1039 to deliver air containing substances. 7. The method according to claim 5, characterized in that the odor-controlling compound is in the form of an indoor air freshener used. 8. The method according to claim 7, characterized in that the indoor air freshener is used in an aerosol will. 9. Means according to claim 1, characterized in that η is 2. 10. The method according to claim 5, characterized in that η is 2. 11. Composition according to claim 9, characterized in that the odor-controlling compound 3-cyclohexenylmethylformate. 3-cyclohexenyl methyl acetate, 3-cyclohexenyl propionate, 3-cyclohexenyl methyl isobutyrate, Is 3-cyclohexenylmethyl butyrate or 2- (cyclohex-3'-en-1'-yl) -2-propyl acetate. 12. The method according to claim 10, characterized in that 3-Cyclohexenylmethylformate is used as the odor-controlling compound, 3-cyclohexenyl methyl acetate, 3-cyclohexenyl propionate, 3-cyclohexenyl methyl isobutyrate, 3-cyclohexenylmethylbutyrate or 2- (cyclohex-3'-en-1'-yl) -2-propyl acetate is used. 809851/1039