JPS6044937B2 - Bad odor treatment method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for treating unpleasant odors, and more particularly to a method for eliminating certain malodors.

The art of perfume making probably began in the cave-dwelling of prehistoric humans.

From their inception until relatively recently perfumers have used natural flavor chemicals of animal and plant sources. That is, natural fragrance chemicals such as essential oils such as rose oil and fragrant oil and animal secretions such as sycamore aroma have traditionally been used by perfumers to obtain various fragrances. However, more recently, fragrance researchers have used this technology to develop synthetic fragrances with particularly desirable properties. These synthetic fragrance chemicals have added a new dimension to the art of fragrance production. This is because the compounds produced usually have stable chemical properties and are inexpensive compared to natural flavor chemicals, and such natural flavor chemicals are typically complex substances that cannot be analyzed chemically.
This is because, as a mixture, they are easier to handle than natural flavoring chemicals. In further contrast, synthetic fragrance chemicals have a known chemical structure and therefore can be manufactured by perfumers to meet specific needs. Such requirements are diverse over a very wide range of categories. There is therefore a great need in the art of aroma compositions for compounds with specific olfactory properties. Traditionally, major efforts in the fragrance technology field have been directed toward providing methods for dealing with odors that are unpleasant to the human olfactory sense.

Such odors include bathroom odors, kitchen odors, body odors,
It includes a variety of odors, such as the smell of smoking. Many products have been developed to eliminate these odors. So-called "room fresheners" or "room deodorizers" are examples of such products. Generally, these products have provided concealment through one of two mechanisms.

Masking fragrances are provided either by providing a higher amount of a more desirable fragrance to suppress the unpleasant odor or by providing a fragrance that mixes with the unpleasant odor to provide a different, yet more desirable, fragrance. . Unfortunately, in both cases a large amount of fragrance must be used, which in itself is often unpleasant. Moreover, unpleasant odors can still be detected even at masking fragrance levels that are usually reasonably tolerable. Compositions and methods for unpleasant odor removal that substantially eliminate such odors without the disadvantages mentioned above are therefore particularly desirable. Particularly noxious odors are caused by compounds that have a significant tendency to either donate or accept protons.

Such compounds will hereinafter be referred to as "malodors."
These include lower carboxylic acids, thiols, thiophenols, phenols, lower amines, phosphines, and arsines, all of which are notorious for their odor.
Compounds included. Previously, 4-cyclohexy-4-methyl-2-pentanone was found to have the ability to eliminate such malodors.

Also, prior to this invention, the ability to remove bad odors was not possible! Although not seen, the following compounds have been described in the literature.

Cyclohexyl methyl ketone [see JACSLl5l8 (1952)] Cyclohexyl ethyl ketone [Ber. 2230 (1909)] cyclohexyl isopropyl ketone [JACS? , 880 (196
0)] Cyclohexyl n-propyl ketone [Compt. See Rendorihon 772 (1911)]
Cyclohexyl n-butyl ketone [JACS? , 880
(1960)] 2-methylcyclohexylmethylketone [Arln. See Chim■, 543 (1968)]3
-Methylcyclohexylmethylketone [Bull. sO
．． chlm. 598 (1947)] 4-methylcyclohexylmethylketone [Callad. J. Chem
．． See Fox 1073 (1968)] The present invention provides novel uses for compounds and compositions that are particularly useful for their malodor removal capabilities.

Furthermore, some of these compounds are new compounds. Compounds exhibiting this remarkable ability to eliminate malodors have the following structural formula: with the proviso that the total number of carbon atoms in A..B and C is not more than 5, and R1 represents an alkyl group having 1 to 4 carbon atoms).

As used herein, the term "remove (a malodor)" refers to an odor and/or an effect of a malodor on a person's senses that results in a reduction in the unpleasantness of the malodor to the human olfactory sense. shall be.

This term should not be limited to any particular mechanism by which such results are obtained. The compound useful in the present invention, such as the above (1), can be produced as represented by the following formula.

In the above formula, A. ．． B. C and R1 have the above definitions. Substituted or unsubstituted benzenes as shown in formula (1) are preferably acylated with an acyl chloride under Friedel-Crafts conditions to form the corresponding phenyl alkyl ketone. As shown in formula (■), this phenyl alkyl ketone is hydrogenated over a suitable catalyst, preferably a rhodium metal containing catalyst, to produce the corresponding alkylated cyclohexylmethanol. Oxidation of this alcohol by the BrOwn-Garge method using, for example, chromic acid produces the desired ketone shown in formula (■). Compounds such as those described above useful in the method of the present invention can effectively eliminate malodors when used in small amounts and in many different media.

Room fresheners or Particular preference is given to use in room deodorizers. Other exemplary uses include cleaning agents, powders,
Clothing as applied by washing machine use in liquids, brighteners or fabric softeners or by other applications such as in cupboard incense sticks, cupboard aerosol sprays or clothes storage. In deodorizers, e.g. in paper towels, bathroom tissue paper, sanitary napkins, towels, disposable wipes, disposable diapers and bathroom accessories such as toilet deodorizers, e.g. disinfectants and cleaning agents such as toilet bowl cleaners. antiperspirants and underarm deodorants, systemic deodorants or e.g. hairsprays, hair conditioners, in powder, aerosol, liquid or solid form, for example.
Hair care products such as conditioners, hair colors and dyes, permanent waves, hair removers, hair straighteners, hair styling applications such as pomades, creams, lotions, etc., such as S-selenium sulfide, coal tar. , medicated hair care products or jump agents containing ingredients such as salicylates or foot care products such as foot powders, liquids or colognes, post-shave lotions and body lotions or soaps and In cosmetics, for example synthetic detergents in bar, liquid, foam or powder form, in odor control during manufacturing processes, for example in the textile finishing industry and in the printing industry (inks and vapors), in the pulp industry, for example.
In odor control, such as in storage and processes involved in meat processing, sewage treatment or garbage disposal, or in product odor control, such as in textile finishing products, rubber finishing products, calf leathers, etc.
For example in kennel and pet care products and livestock and pet care products such as deodorizers, jumping agents or cleaning agents or animal bedding materials, for example in theater auditoriums, subways and transport. Exists in large-scale closed air systems such as engines. It has been found that the amount of the compound that can be used is generally independent of the particular malodor involved.

Similarly, it has been found that the concentration of the malodor in the air does not determine the effective amount of the compound used. A suitable amount should be used to eliminate malodors. However, the amount of any such compound will depend on the medium in which it is used, temperature, humidity, amount of air and air circulation. Generally, such compounds are effective when present in air (containing malodors) at levels as low as about 0.01 mg per cubic meter of air. Some compounds are more active than others, depending, of course, on the structure of the particular compound used.
Any concentration above the above amounts is generally effective. However, in practice, more than about 1.0 to 2.0 m9 per cubic meter of air is probably unnecessary. The novel compounds useful in this invention are 4-ethylcyclohexylmethylketone and 4-isopropylcyclohexylmethylketone.

Particularly preferred compounds useful in the invention are those where AlB and C are hydrogen and/or R1 is methyl.

Particularly preferred compounds are cyclohexylmethylketone and 3-methylcyclohexylmethylketone. Specific examples of other compounds useful in the present invention include, for example, 4-tertiary butyl cyclohexyl methyl ketone, 4
-isopropylcyclohexylmethylketone, 2-methyl-4-tert-butylcyclohexylmethylketone, 2
-Methylcyclohexylmethylketone, 2-methyl-5-isopropylcyclohexylmethylketone, 4-methylcyclohexylisopropylketone, 4-methylcyclohexyl sec-butylketone, 4-methylcyclohexylisobutylketone, 2●4-dimethylcyclohexylmethylketone, 2 ●3-dimethylcyclohexylmethylketone, 2●2-dimethylcyclohexylmethylketone, 3,3-dimethylcyclohexylmethylketone, 4●4-dimethylcyclohexylmethylketone, 3●
Mention may be made of 3.5-trimethylcyclohexylmethylketone and 2.2.6-trimethylcyclohexylmethylketone.

Next, the present invention will be explained in detail with reference to Examples.

Specific descriptions in the examples should not be construed as limiting the scope of the invention. Symbol "K9lpo"
is the weight of the substance present in 1 cubic meter of air (Mg
) means. Example 1 Cyclohexyl Methyl Ketone Cyclohexyl methyl ketone is produced in small amounts as a by-product in the hydrogenation of acetophenone to 1-cyclohexylethanol.

Purification of 1-cyclohexylethanol by fractionation produces an initial distillate rich in cyclohexylmethylketone (this is
(also contains cyclohexylethanol).
A representative initial distillate containing 38.5y (0.3 mol) of 1-cyclohexylethanol and 21.3y (0.1688 mol) of cyclohexyl methyl ketone was added to 200 ml of
diluted with acetone and cooled in an ice bath for 15-20 min.
At ℃? Oxidized with 75mt(7)8N chromic acid (Jones reagent) in sulfuric acid.

Isolation was accomplished by decanting the upper organic layer and concentrating it on a rotary evaporator.

The concentrated chromium sulfate solution was diluted with water and extracted with ether. To this extract was added the concentrate from the evaporator. The resulting ethereal solution was thoroughly washed with water, concentrated sodium bicarbonate solution and brine and evaporated on a rotary evaporator to yield 53.4y cyclohexyl methyl ketone (99.35% by GLC) with a chemical fruit aroma. pure). n 5 = 1.45000 NMR spectrum is 1.33
and two broad multiplets (cyclohexyl protons) at 1.73 ppm and one? 2. Indicates -CG3 group.
It had a single line at 00 ppm. Example 2 21.4y(a). of cyclohexylethylketone in 150ml of ether. 1
5 mol) of 1-cyclohexy-1-propanol with stirring and cooling in an ice solution at 15-20°C.
75 mt(7) 2N chromic acid (BrOWIl-Garg reagent) was added at a rate such that the temperature was maintained at .

After the addition was complete, the ice bath was removed and stirring continued for 30 minutes. IR
Analysis and GLC analysis confirmed that all starting material was consumed. A similar isolation procedure as described in Example 1 yielded 19.4y of crude cyclohexylethyl ketone (n?
5=1.4508) was obtained.

It contained small amounts of low boiling impurities, which were removed by distillation through a short Vigreux column. 0.9y
First boiling point (boiling point 60-62℃/5WILHg..n 5=
1.4500), the product cyclohexylethyl ketone is a colorless, aromatic (strongly chemical) liquid with a boiling point of 67.
Collected at C/5 RoHg.

Is this n? = 1.4506 (purity 99.2%, by GLC). Yield 15.5y (73.7%). Example 3 Cyclohexylisopropylketone An industrial grade 1-component consisting of 8.15y of cyclohexylisopropylketone and 17.85V (0.1142 mol) of 1-cyclohexyl-2-methyl-1-propanol
The first distillate obtained from the fractionation of cyclohexy-2-methyl-1-propanol was dissolved in 120 mL of ether and treated with 58 ml (7) of 2N chromic acid solution (BrOwn-Garg reagent) at 15-20°C.

The oxidation was complete after 3 gins. 25.7 g of crude cyclohexyl isopropyl ketone (n=1.4489) essentially pure by isolation procedure similar to that described in Example 1
I got it.

Traces of low boiling impurities were removed by distillation through a short Vigreux column. 2.2y initial distillation (boiling point 35-38 C/0.8Tr0rLHg..nBa3=1.4475)
After that, cyclohexyl isopropyl ketone turns into a colorless, aromatic (fresh, pungent, peppery) liquid (n3=1.
4490) at a boiling point of 38°C/0.8Tm1nHg.

Yield 22.7y (according to α℃) with purity 99.6%
82.6%) was obtained. Example 4 Cyclohexyl n-propyl ketone An industrial 1-cyclohexyl ketone consisting of 15.0y (0.096 mol) of 1-cyclohexyl-1-butanol and 15.5y (0.101 mol) of cyclohexyl n-propyl ketone
The first distillate obtained from the fractionation of cyclohexy-1-butanol was dissolved in 150 Tn1 of ether and
50 mL (0.1 mol) of Δchromic acid (Br
Own-Garg reagent).

The reaction was rapid, highly exothermic and quantitative in nature. A similar isolation procedure as described in Example 1 (including washing the crude ketone-containing ether solution with sodium bicarbonate solution to further remove the dark amber color) yielded the crude cyclohexyl n-propyl 29.7y. Got ketones.

The yield was 96.3%, n? 3=1.4505.
An initial distillation of 2.8 V (boiling point 30-38°C/0.8 WLHg1n=1.
4454) and cyclohexyl n-propyl ketone was obtained by GLC analysis as a colorless aromatic substance (
Fresh chemical ether system) was collected as a liquid at C/0.8TrrInHg with boiling point 38-44. NK=1.
4515. The yield was 25.7q (83.3%).
Example 5 13.7 V(a). of 40 ml of cyclohexyl n-butyl ketone in ether. 08
A solution of 1-cyclohexy-1-pentanol (mol) was oxidized with 40 mL of 2N chromic acid solution (BrOWTl-Gamg reagent) at 15-20 °C.

By isolation procedure similar to that described in Example 1, 12.11y
Crude cyclohexyl n-butyl ketone was obtained.

During the fractionation through the Holtzmann column, the middle distillate (boiling point 10
5℃/9w$THg) was collected, which was 1-cyclohexyl n-1''butyl ketone obtained as a colorless aromatic (balsam-like woody) liquid (n=1.4538).The yield was 8.2y.Example 6 13.2y(a).09 in 50ml of 2-methylcyclohexylmethylketone in ether
A solution of 28 mol) of cis/trans-1-(2-methylcyclohexyl)-1-ethanol is cooled in an ice bath and added to it with 50 ml of bochromic acid solution (BrOwn) at a rate to maintain the temperature at approximately 10°C. -Garg reagent) was added dropwise with stirring.

After the addition was complete, the ice bath was removed and stirring continued for 1 hour at ambient temperature. A similar isolation procedure as described in Example 4 yielded 9.95y of crude 2-methylcyclohexylmethylketone as a colorless liquid (76.4%), which was purified by distillation through a short Vigreux column.

2-Methylcyclohexylmethylketone was collected as a middle distillate (boiling point 720C/8 Hg..n?=1.4552).

It was a colorless, aromatic (mushy, fresh chemical) liquid. The yield was 8.55q (65.8%). Example 7 13.2f (0.09
28 mol) cis/trans-1-(3-methylcyclohexyl)-1-ethanol solution in 52mt(7)2N
Oxidized with chromic acid solution (BrOwn-Garg reagent) and isolated as described in Example 6.

101.6y (77%) with 96% purity by GLC.
6%) of 3-methylcyclohexylmethylketone was obtained. This is refined by distillation through a short Vigreau column to produce substantially pure cis/trans-3-methylcyclohexylmethylketone, a colorless, aromatic (chemically irritating ether-based) liquid (boiling point: 59°C/100T$LHgn). 1.4489). The yield is 7.13q (5
4.9%). Example 8 14.4y (0.101
A solution of 4 mol) of cis/trans-1-(4-methylcyclohexyl)-1-ethanol was oxidized with 52 ml of Δchromic acid solution and isolated as described in Example 6.

Crude 4-methylcyclohexylmethylketone was obtained in a yield of 12.0 Da (84.0%) with 99.0% purity by GLC. Continue to distill this further and 9.1
y (64.1%) of 4-methylcyclohexylmethylketone (boiling point 54°C/9.5wnHg1nBa5 = 1.4
500) was obtained as a colorless, aromatic (fresh, fishy and strong)-liquid. Example 9 15.9y (0.101
9 mol) of cis/trans-1-(4-ethylcyclo.
Hexyl)-1-ethanol solution 50Tn1(7)
Oxidized with 2N chromic acid solution (BrOwn-Garg reagent) and isolated as described in Example 6.

The crude product (16.2y=103%) was purified by distillation over 0.133 da boric acid. Substantially pure cis/trans-4-ethylcyclohexylmethylketone (boiling point 9
1℃/9.5TmHg. ．． n? = 1.4541). It was a colorless, aromatic (chemical and pungent) liquid.
Example 10 15.1 g (0.0
887 mol) of cis/trans-1-(4-isopropylcyclohexyl)-1-ethanol in 50ml
Δchromic acid solution (BrOwn-Gamg reagent) and isolated as described in Example 6 to give 14.15y.
Crude cis/trans-4-isopropylcyclohexylmethylketone was obtained. The yield was 95.7%. The product was purified by distillation through a short Vigreux column. The recovered colorless, aromatic (fresh, pungent, yeast-like) liquid of 4-isopropylcyclohexylmethylketone has a boiling point of 59-60°C/0.8wr! NHg and self 5
=1.4573. Example 11 The following malodor concentrates were prepared.

Bathroom odor concentrate Ingredients Parts by weight Skatole 0.91 β-thionaphthol 0.91 95% aqueous solution of notioglycolic acid 21.18 n-caproic acid
6.00 p-cresyl isovalerate 2.18 N-methylmorpholine 6.00 dipropylene glycol 62. Aerosol cans having the above malodor were prepared at concentrations of 82 or higher.

Bathroom odor aerosol Ingredients Parts by weight Solution chamber odor concentrate 0.1 Dipropylene glycol 4.9 Propellant (a) Trichloromonofluoromethane 47.5 (b) Dichlorodifluoromethane 47.5 "SpicefOrCQlOgne" fragrances were selected for use in malodor removal testing of test compounds.

The fragrance of the "fragrance for eau de cologne" contained the following ingredients. Ingredients Parts by weight Lavandin abrialis oil 60 amyl cinnamaldehyde 20 amyl salicylate
150 benzyl acetate
30 linalool
30 cedar wood oil
10 Geraniol 130 Isopulegol 60 Methyl anthranilate (1 volume % solution in dipropylene glycol)
20 musk xylol
60 Coumarin 50
Phenylethyl acetate 30 Tervinyl acetate 100 Katsura leaf oil
40 Butygrain oil SA6O Ylang Ylang oil 130 Phenyl acetaldehyde dimethyl acetal
15 cinnamon alcohol
An aerosol can was prepared using the above fragrance composition containing the compounds shown in Table 1 as follows.

Weight % "Fragrance for Eau de Cologne" Fragrance 0.45; Compound to be tested 0.05 Propellant (a) Trichloromonofluoromethane 49.75 (b) Dichlorodifluoromethane 49.75100.
00, with inlet door and exhaust fan, total capacity 29
．． 9d and the inner dimensions are 3.35X3.66X2.4
A test chamber with 4 (7T1,) was prepared.

The capacity of the exhaust fan was 14 d/min. A 5-minute evacuation period between tests to ensure sufficient evacuation. Once the Anne was operated and before conducting the next test, an odor check was made to see if any residual odor could be detected. After the test chamber was properly evacuated, the bathroom odor was sprayed with an aerosol can for approximately 5 seconds.

After 10-1 minutes, the fragrance composition aerosol was sprayed for about 5 seconds (5 seconds being the average time such an aerosol would normally be used by a housewife).

After 1 minute, two judges (one skilled in perfumery and odor evaluation, and the other with no such skills other than knowledge of fragrances in general) ) entered the test room, conducted an odor evaluation for malodor detection, and recorded the sensing results.

All tests were conducted without any examiner knowing what substance was being tested. Based on the flow rate through the valve used in the aerosol can, the approximate volume of arosol containing malodorous concentrate introduced into the test chamber was 267 m91
It is d.

The amount of aerosol containing the fragrance composition introduced into the test chamber is approximately 260 m9 nod. Table 1 Using the above test procedure
Compounds shown in Table 1 were tested for their ability to remove bathroom odors.

Yoshika is shown in Table 1. In the above, the malodor removal ability of the compound is shown by the following Danji evaluation criteria.

U)l (“Noticeable” - fresh air effect is significant and produces very slight residual odor or no residual odor)
"Excellent" - There is a fresh air effect and a slight pleasant residual odor (background) ■ "Very Good" - There is no fresh air effect, but all bad odors are removed,
There are various degrees of residual original odor, but not too high. ``Good''
There is a trace of bad odor, often of a changed quality, and there is a residual original odor that is not too strong but pleasantly tolerable.
``Very good'' - Not strong, but clearly distinguishable and distinctive odor, with an acceptable residual odor Y. ``Poor'' - Slightly reduced intensity, but overwhelmingly distinct There is a foul odor and an unacceptable and unpleasant residual odor is present throughout.

Z "No effect" Although the invention has been described herein with respect to certain specific embodiments, the invention is not limited thereto.

Claims (1)

[Claims] 1. Structural formula of malodor removing action ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, each of A, B and C independently represents hydrogen or 1 to
represents a lower alkyl group having 4 carbon atoms, provided that the total number of carbon atoms in A, B and C is not more than 5, and R^1 represents an alkyl group having 1 to 4 carbon atoms; A method of treating malodors for reducing their unpleasant odors, which comprises treating malodor-containing air with a compound represented by (representing a group). 2. The method of paragraph 1, wherein the malodor-removing dose is at least 0.01 mg per cubic meter of malodor-containing air. 3. The method of item 1 above, wherein A, B and C are each hydrogen. 4. The method of item 1 above, wherein R^1 is methyl. 5. The method of item 3 above, wherein the compound is cyclohexylmethylketone. 6. The method of item 4 above, wherein the compound is 3-methylcyclohexylmethylketone.