US3326746A

US3326746A - 1, 3-dioxane cleaning compositions

Info

Publication number: US3326746A
Application number: US221318A
Authority: US
Inventors: Cahn Arno; Allan H Gilbert
Original assignee: Lever Brothers Co
Current assignee: Lever Brothers Co
Priority date: 1962-09-04
Filing date: 1962-09-04
Publication date: 1967-06-20
Anticipated expiration: 1984-06-20
Also published as: GB981285A; US3423430A

Description

United States Patent 3,326,746 1,3-DIOXANE CLEANING COMPOSITIONS Arno Calm, Pearl River, N.Y., and Allan H. Gilbert, West Englewood, NJ., assignors to Lever Brothers Company, New York, N.Y., a corporation of Maine No Drawing. Filed Sept. 4, 1962, Ser. No. 221,318 16 Claims. (Cl. 167-17) This invention relates to a perfume. More particularly, it relates to a cleaning product with this perfume therein.

It is known that natural geranium oil may be used as a perfume. However, the natural oil is a complicated mixture of numerous components and it has not been possible, heretofore, to form a synthetic product with a suitable geranium note. Even blends prepared by combining the known components of the natural oil do not have the proper odor characteristics.

It is also known to incorporate a perfume into a cleaning product, e.g., a dishwasher product. If, however, the cleaning product contains a chlorine-releasing agent, the prior art perfumes are not satisfactory since they do not overcome the pungent odor resulting from the use of this product. For example, an unsaturated perfume may lose its odoriferous properties and stability because the unsaturation is attacked by the chlorine-releasing agent.

It has now been discovered that a synthetic perfume may be prepared which has a satisfactory geranium-rose note. Furthermore, this perfume may be advantageously employed in cleaning products including those products having chlorine-releasing agents therein. Such a perfume has the following generic structure:

wherein R is an alkyl group having 4 to 9 carbon atoms; R is selected from the group consisting of hydrogen and a C to C alkyl group; and R is selected from the group consisting of hydrogen and methyl.

It is important for the success of the present invention to have a 1,3-dioxane with alkyl groups in at least the 2,4 positions. If R were the only alkyl group, such as isobutyl or l-ethylpropyl, the compounds therefrom would be devoid of any geranium-rose note. The number of carbon atoms in R is also important; there must be at least 4 carbon atoms but not more than 9 carbon atoms in a straight or branched chain. For example, if R were isopropyl or decyl, the resulting compound would not possess the required geranium-rose note.

Another important feature lies in the 4-methyl substituent in the above structure. The desired perfume would not be provided it higher alkyls, such as ethyl and isopropyl, were employed. Each of the ring carbons must have at least onehydrogen thereon. If a gemdialkyl group is located on any of the ring carbons, the compounds therefrom do not have a geranium-rose note.

The 2,4-dialkyl-l,3-dioxanes of the present invention may be prepared in accordance with similar procedures known in the art for forming other 1,3-dioxanes. Generally about lsto 1.5 equivalents of a 1,3-diol are reacted with about 1 equivalent of an aldehyde in the presence of, firstly, a solvent which azeotropes with water, e.g., chloroform, ethylene dichloride and benzene, and, secondly, about 0.01% to about 10% of an acid catalyst, e.g., sul- LXAMINLN':

3,326,746 Patented June 20, 1967 furic acid, hydrochloric acid, p-toluenesulfonic acid and an insoluble resin acid of the sulfonic acid type. The temperature of the reaction is not critical but it is generally maintained between about 40 and 150 0, preferably between about 60 and 100 C.; time varies inversely from about 1 to 6 hours. Water is removed until the reaction is complete with subsequent cooling; neutralization with aqueous alkali, dry alkali, sodium carbonate or the like; washing; and distillation to provide the desired dioxane.

With respect to a second embodiment of this invention, the 2,4-dialkyl-1,3-dioxanes having the geranium-rose note may be incorporated into a cleaning product, e.g., a dishwasher formulation, to overcome the strong odor resulting from the chlorine-releasing compounds therein. The other ingredients usually included in the instant cleaning products besides the dioxanes and chlorine-releasing agents are soaps or non-soap detergents and phosphates. A cleaning product is broadly defined herein as a substance or a composition which removes undesirable dirt, food particles, stains or the like or which renders an item unsoiled. This, therefore, includes dishwashing compounds, dry bleaches, scouring cleansers, light-duty detergents, heavyduty detergents, pelleted detergents, soap products and scouring pads.

The perfume content depends upon the specific dioxane and the type of cleaning product. Generally, the dioxane perfume is employed in an amount up to about 0.5 part, preferably between about .05 to .25 part, per 100 parts by weight of the total cleaning product (phcp.).

Any chlorine-releasing agent known in the art may be satisfactorily utilized in this invention. A chlorine-releasing agent is defined herein as a chlorine-containing compound which liberates chlorine under conditions normally used for cleaning purposes. These agents may range from 0.5 to 40 parts (phcp.). Examples of suitable chlorine-releasing agents are as follows: chlorocyanurates, chlorinated trisodium phosphate, N-chlorosuccinimide, calcium hypochlorite, and N,N dichloroazocarbonamidine.

Soaps and non-soap detergents, which are usually found in the cleaning products of this invention, are well defined terms of art [Chemistry of Organic Compounds, Noller (1951), pp. 186-90; College Chemistry, Smith (1947), pp. 431-2 and 455]. Any known soap or non-soap detergent is applicable including the following compounds: sodium lauryl sulfate, sodium alkyldiphenyloxide, alkali metal salts of fatty acids and the wetting agents disclosed in US. Pat. No. 2,263,948 which is incorporated herein by reference. These soaps or detergents may comprise about 0.5 to 80 parts (phcp.).

The instant cleaning products generally have an alkali I metal phosphate therein. This terminology covers a well known class of compounds employed in cleaning compositions (US. Pat. No. 2,310,475). The orthophosphates, pyrophosphates, polyphosphates and metaphosphates are applicable to the present invention. These phosphates, e.g., sodium tripolyphosphate, may comprise about 1 to parts (phcp.).

A soil-suspending agent, e.g., sodium carboxymethylcellulose and polyvinyl alcohol, is advantageously added in certatin types of products within the range of about 0.2 to 1.0 parts (phcp.). The following ingredients are also frequently employed: other perfume compounds in combination with the dioxane perfumes; abrasives, e.g., silica; metallic strands (for scouring pads); silicates; carbonates; and borates.

The preferred ranges for the various ingredients in different products are indicated in Table I.

Preferred Range, Percent I In Dishwash- In Dry In Heavy In Scouring Compo- Bleach Duty Detering sitions gents Cleansers Soaps or Nonsoap Detergents:

Sodium lauryl sulfate 1-2 2-4 10-20 2-3 Pluronic L-Gl 3-4 2-4 8-10 4-5 Pluronic L-62 3 3-4 2-4 8-10 4-5 Sodium alkyldiphenyloxidesulfonate 0.6-0.8 2-4 8-10 4-5 Soap. 3-4 2-4 40-80 4-5 Soil-suspending Agents:

Sodium carboxymethylcellulose. 0. 3-0. 5

Sodium carboxymethyl hydroxy ethyl cellulose. 0. 3-0. 5

Sodium cellulose sulfate 0. 3-0. 5

Polyvinyl alcohol- 0. 3-0. 5

Polyethylene glycols- 0. 3-0. 5 Chlorine-Releasing Agents:

Trichlorocyanuric acid 8-10 8-10 4-8 Sodium and potassium dichlorocyanurate. 14-16 14-16 5-10 Dichlorodimethylhydantoiu 14-16 14-16 5-10 N-chlorosuccinimlde 14-16 14-16 5-10 Trichlornmelarnino 14-16 14-16 5-10 Calcium hypochlorite 14-16 14-16 4-8 Chlorinated trisodium phosphate 8-10 8-10 4-8 Chloramine-T L. 14-16 14-16 5-10 N. N-dichloro-azocarbonamidine 14-16 14-16 6-10 Phosphates:

Sodium tripolyphosphate 40-50 5-20 40-50 Sodium Eyrophosphate. 40-50 5-20 40-50 Sodium exametaphosphate. 40-50 5-20 40-50 Sodium tetraphosph ate 40-50 5-20 40-50 Sodium trimetaphosphate (soluble) 40-50 5-20 40-50 Abrasives:

Silica.

Volcanic ash Diatomaceous earth Pumice Alumina Feldspar Carborundum.

Fine metallic particles 6 Metallic strands Plastic web 6 Other:

Sodium metnsilir'ate RU-silicate 6 N-silicate Sodium carbonate..

Sodium tetraborate.

Sodium sesquicarbonate Sodium sulfate (to 100%) X Percentages are based upon cleaning compound before dioxane perfumes are added thereto.

1 Empirical formula H()(cznio)-(C:I-leO)b(CzH40) CH wherein b is selected to provide a mol. wt. of propylene oxide of 1.750 and a+c is an integer to provide 10% ethylene oxide in the molecule.

I Empirical formula HO(C;1l40)-(C;H6O)b(C1lI4O)c1l wherein b is selected to provide a mol. wt. of propylene oxide of 1,750 and a+c is an integer to provide 20% ethylene oxide in the molecule.

The dioxanes heretofore described may also be utilized to perfume cleaning compositions without any chlorinerelcasing agents therein. These compositions include liquid detergent formulations, soaps and toiletry products, especially those that are neutral or alkaline. Furthermore, a bleaching-type product may be formed which contains only a dioxane perfume and a chlorine-releasing agent.

Thus, in accordance with this invention, a synthetic perfume with a suitable geranium-rose note has been provided. Furthermore, it is now possible to manufacture a cleaning product comprising a chlorine-releasing agent and a 1,3-dioxane perfume which can be used without the formation of an objectionable odor.

The following examples are submitted to illustrate but not to limit this invention. Unless otherwise indicated, all parts and percentages in the specification are based on weight.

Example 1 The following compounds were mixed in a 250 ml. flask: 11.4 g. (0.1 mole) of hcptaldehyde; 9.9 g. (0.11

ExampleZ The compounds indicated in Table II were prepared in accordance with similar procedures as described in Example 1.

HHHHHHHHHH mm HHHHHHHHCC HHHHHHHHHH TABLE II Compounds l R1 ges, and the per- Example A dishwasher product was provided with 0.1% 2-isobutyl 4,5,6 trimethyl 1,3 dioxane and the ingredients Parts 44.00 9.60 7.414 5.878 2.25 0.75 0.004 30.104

F. in both closed jars ulation lost none of HHHHHHHHHHHHH ipolyphosphate 1 Chlorinated trisodium phosphate 1 These bleaches were stored for six days at 95 F. in both closed jars and commercial packa fume odor was not affected by the chlorine-releasing agents therein.

shown herebelow:

Ingredient:

Sodium tr N-silicate 1 RU-silieate Pluronic L62 Pluronic L61 Colorants Water 1 Expressed on dry basis. After storage for six days at 95 and commercial packages, this form its perfume odor.

-rose duct Parts Example 6 TABLE III Example 3 Example 4 Dry chlorinated bleaches were formed with the following ingredients therein.

dioxane.

All of the above compounds possessed a geranium note and were suitable for incorporation into a pro The compounds listed in Table III were prepared but they did not exhibit a geranium-rose note.

Compounds R1 This example demonstrates the criticality of the substituents on the 1,3 dioxanes in order to provide the de- Ingredient ptyl-4-methyl-l,3-dioxane.

containing a soap or non-soap detergent and a chlorinereleasing agent.

sired odoriferous properties.

2-isobuty1-4-methyl-1,3-dioxane 2-n-he 2-isobutyl-4,6-dimethyl-1 .3-

Percent lbenzenesulfonate 10 Sodium xylenesulfonate 8 LDA 1 2.7

y alcohol sulfate. Potassium dichlorotriazinetrione a 1: 1 mixture of alkylbenzene sulfonates in which the al f 1propylene group and has an average of 12 and 15 carbon ive y.

lhydantoin.

1 Primarily portion is a poly Dichlorodimethy Sodium tatt Sodium tripolyphosphate.-

Sodium sulfate- Sodium alkylbenzenesulionate Halaue atoms respec The perfume odor of this formulation was unaffected after being stored in accordance with the procedure described in Example 4.

Example 7 The scouring cleanser-type formulation indicated herebelow was perfumed with 0.1% of 2-isobutyl-2,4-dimethyl- 1,3-dioxane.

Composition: Parts Silica, 90 mesh 70 Chlorinated trisodium phosphate Sodium alkylbenzene sulfonate 3.33 Sodium tripolyphosphate 16.67

After storage, as per Example 4, the perfume odor was unaffected.

Example 8 Two perfumery blends were provided. Blend A contained 20% of 2-isobutyl-4-methyl-1,3-dioxane as the principal source of geranium odor. Blend B had conventional perfumery materials as the source of geranium character. The blends had the following composition:

Parts Composition Citronellol 200 200 2-isobuty1-4-methyl-1,3-dioxane 200 Cinnamic Alcohol 500 600 Thyme Oil 30 30 Amy] Cinnnmic Aldeh 40 40 Linelool 100 Geronyl Acetate 100 Total 970 970 The dishwasher product in Example 6 was modified independently with 0.05% of each blend. After storage as described in Example 4, the odor of Blend A remained unchanged. Conversely, the product with Blend B had less geranium odor after storage.

Having set forth the general nature and specific embodiments of the present invention, the true scope is now particularly pointed out in the appended claims.

What is claimed is:

1. A composition comprising a chlorine-releasing agent selected from the group consisting of trichlorocyanuric acid, chlorocyanurates, chlorinated trisodium phosphate, N-chlorosuccinimide, calcium hypochlorite, N,N-dichloroazocarbonamidine, dichlorodimethylhydantoin, trichloromelamine and sodium derivative of N-chloro-p-toluene sulfonamide and a 1,3-dioxane having the structure:

wherein R is an alkyl group having 4 to 9 carbon atoms; R; is selected from the group consisting of hydrogen and a C to C alkyl group; and R is selected from the group consisting of hydrogen and methyl.

2. A cleaning composition comprising a member selected from the group consisting of a soap and a non-soap detergent, a chlorine-releasing agent selected from the group consisting of trichlorocyanuric acid, chlorocyanurates, chlorinated trisodium phosphate, N-chlorosuccinimide, calcium hypochlorite, ZN,N-dichloroazocarbonamidine, dichlorodimethylhydantoin, trichloromelamine and sodium derivative of N-chloro-ptoluene sulfonamide, an alkali metal phosphate and a 1,3-dioxane having the structure:

3. The composition according to claim 2 in which the dioxane is 2-hexyl-4-methyl-1,3-dioxane.

4. The composition according to claim 2 in which the dioxane is 2-n-butyl-4-methyl-1,3-dioxane.

5. The composition according to claim 2 in which the dioxane is 2-(1-ethylpropyl)-4-methyl-1,3-dioxane.

6. The composition according to claim 2 in which the dioxane is 2-(l-methylbutyl)-4-methyl-1,3-dioxane.

7. The composition according to claim 2 in which the dioxane is 2-(2-ethylamyl)-4-methyl-l,3-dioxane.

8. The composition according to claim 2 in which the dioxane is 2-n-heptyl-4-methy1-1,3-dioxane.

9. The composition according to claim 2 in which the dioxane is 2-n-octyl-4-methyl-1,3-dioxane.

10. The composition according to claim 2 in which the dioxane is 2-i-butyl-4-methyl-1,3-dioxane.

'11. The composition according to claim 2 in which the dioxane is 2-i-butyl-4,5,6-trimethyl-1,3-dioxane.

12. The composition according to claim 2 in which the dioxane is 2-i-butyl-4,5-dimethy1-1,3-dioxane.

13. The composition according to claim 2 in which the dioxane is 2-i-butyl-4,6-dimethyl-1,3-dioxane.

14. A dishwasher composition comprising sodium tripolyphosphate; chlorinated trisodium phosphate; a sodium silicate containing a SiO :Na O ratio of 2.4; a sodium silicate containing a SiO :Na O ratio of 3.25; a first deter-gent compound with an empirical formula HO(C H O) (C l-I ,'O) ,(C H.,O) wherein b is selected to provide a molecular weight of 1750 for propylene oxide and a+c is an integer selected to provide about 10% ethylene oxide in the molecule; a second detergent compound with an empirical formula 2 4 )a( 3 6 )h( z 4 )e wherein b is selected to provide a molecular weight of 1750 for propylene oxide and a+c is an integer selected to provide about 20% ethylene oxide in the molecule; and a 1,3-dioxane having the structure:

wherein R is an alkyl group having 4 to 9 carbon atoms; R, is selected from the group consisting of hydrogen and a C, to C alkyl group; and R is selected from the group consisting of hydrogen and methyl.

5 15. The composition according to claim 14 in which the dioxane is 2-isobutyl-4,5,6-trimethyl-1,3-dioxane.

16. The composition according to claim 14 in which the dioxane is 2-isobuty1-4-methyl-1,3-dioxane.

10 References Cited UNITED STATES PATENTS 2,684,373 7/ 1954 Patrick 260340.7 3,042,621 7/ 1962 Kirschenbauer 252-99 3,057,877 10/1962 Klein 260340.7 3,110,677 11/1963 Karabinos 252-99 ALBERT T. MEYERS, Primary Examiner.

A. P. FAGELSON, Assistant Examiner.