PREPARATION OF A GLUTARALDEHYDE PRECURSOR

Abstract: Described herein is a process for the preparation of a novel essentially nonaqueous glutaraldehyde precursor which is capable of rapidly generating glutaraldehyde upon addition to water. The precursor is prepared by the hydration of 2-alkoxy-3,4-dihydropyran in the presence of an acid catalyst.

Description: This invention is directed to a process for the preparation of a novel essentially nonaqueous glutaraldehyde precursor which is capable of rapidly generating glutaraldehyde upon addition to water. The precursor is prepared by the hydration of 2-alkoxy-3,4- dihydropyran in the presence of an acid catalyst. Clutaraldehyde is widely used in many appli cations, such as leather tanning, embalming, photography and particularly as a microbiocide. Glutaraldehyde is generally prepared by -the acid hydrolysis of 2-alkoxy3,4-dihydropyran in a system containing a large excess of water. Without water, glutaraldehyde is generally not stable and polymerizes to a glassy-mass on standing. Thus, it is always prepared as an aqueous solution. A commercial concentration generally contains from about 50 to about 98 percent water. However, even this aqueous glutaraldehyde solution is capable of polymerizing to an oligomer andlor to a polymer which precipitates from the aqueous solution on standing. Further, glutaraldehyde undergoes an algol condensation. The formation of these condensation products, as well as oligomers and/or polymers increases with, for example, increasing temperature, glutaraldehyde concentration, and pH. The current processes for preparing glutaraldehyde have drawbacks. The formation of the condensation products and/or oligomers and polymers results in the loss of glutaraldehyde. Also, the use of 50 percent or more of water during the acid hydrolysis of the 2alkoxy-3,4-dihydropyran decreases reactor capacity. Further, when the commercial 50 percent aqueous solution is shipped to warm climates, thermal stability of the solution becomes a serious problem. Also, in cold weather the aqueous solution may freeze. Thus, there is much interest in developing a nonaqueous precursor to glutaraldehyde capable of yielding glutaraldehyde upon its addition to water. Such a precursor could be stored or shipped in varying climates without the resulting problems now associate2 with an aqueous solution. U.S. Patent 4,244,876 describes the formation of a precursor to glutaraiehyde, i,e., x,6,dimethoxytetra hydropyran. It is prepared by the addition of an alcohol to 2-methoxy-3,4-dihydropyran. However, the conditions under which the glutaraldehyde is produced from the 2,6 ditnethoxytetrahydropyran are time consuming, since it requires several hours at low pH to generate a substantial amount of glutaraldehyde. U.S. Patent 2,546,018 describes the preparation of glutaraldehyde by heating a derivative of dihydropyran, for example, a 2-alkoxy-3,4-dihydropyran with water. The principal product of the reaction is glutaraldehyde. Thus, the problems associated with aqueous or nonaqueous glutaraldehyde still exists. In the present invention a novel essentially nonaqueous glutaraldehyde has been discovered. THE INVENTION This invention is directed to a process for the preparation of a novel essentially nonaqueous glutaraldehyde precursor. The precursor is prepared by hydrating 2-alkoxy-3,4-dihydropyran in the presence of an acid catalyst at a temperature of from about 30 to about 100 C and wherein the molar ratio of water to 2alkoxy-3,4-dihydropyran is from about 1:1 to about 3:1. The hydration conditions are such that materials containing appreciable and substantial carbonyl content are not produced, i.e., essentially no free glutaraldehyde is produced. The hydration product produced does not polymerize, Also, it has better thermal stability and a lower freezing point than a commercial 50 percent or greater glutaraldehyde solution. The hydration product yields glutaraldehyde upon addition to water. The reaction may be illustrated by the hydration of, for example, 2-methoxy-3,4-dihydropyran: EMI3.1 The principal product is 2-hydroxyl-6-methoxy tetrahydropyran (I) although trace amounts of 2,6dimethoxytetrahydropyran (II) glutaraldehyde (III) and their isomers are formed. The reaction is carried out in the presence of an acid catalyst. The acid catalyst may be an inorganic or an organic acid or an ion exchange resin. The acids which may be used herein include a strong mineral acid, an acid-reacting salt, a material which will react under the conditions of the process to for in situ, an acid-reacting material or a supported acid catalyst. These acid catalysts include phosphoric acid, hydrochloric acid, sulfuric acid, trifluoromethylsulfonic acid, para-toluenesulfonic acid, as well as supported acid catalysts, such as Amberlyst which is a supported arylsulfonic acid (sold by Rohm & Haas Company) and Nafion which is a supported fluorosulfonic acid (sold by 5. I. duPont de Nemours Co.). When a liquid acid is used, the acid may be removed after hydration by neutralizing it with a base to form a salt and then removing the salt, as by filtration. The reaction is carried out at a temperature of from about 30 to about 100"C, and preferably from about 40 to about 90"C. The reaction temperature and time are dependent upon the type and amount of catalyst used in the reaction. The reaction is generally carried out ct atmospheric pressure, although subatmospheric and super atmospheric pressures may be used. The molar ratio of water to 2-alkoxy-3,4-di hydropyran in the reaction is from about 1:1 to about 3:1, and preferably from about 1:1 to about 2:1. The use of larger amounts of water offer no advantages since reactor capacity is reduced and the shelf-life of the reaction product is reduced. The alkoxy group of the 2-alkoxy-3,4-dihydro- pyran preferably contains from 1 to 3 carbon atoms. The reaction product may be used as such. It is added to water to produce glutaraldehyde. The water may contain optional ingredients such as colorants, thickeners, fragrances, and the like. However, water is the predominant material. EXtHPLES The following examples serve to give specific illustrations of the practice of this inxFen- tion but they are not intended in any way to limit the scope of this invention. Example 1 A 250 ml 4-necked round bottom flask, fitted with a condenser, a mechanical stirrer, a thermometer and a nitrogen inlet was used as the reaction vessel. The flask was flushed with nitrogen and 114 g. of 2-methoxy-3,4-dihydropyran, 21.6 g. of distilled water and 13.2 of Rexyn 101, a sulfonated polystyrene (supplied by Fisher Scientific Co.) were added. Tha catalyst resin was rewashed with distilled water ro remove most of the water soluble acids which might be present. The resin contained 5 rnilliequivalents,ot acid per gram of dry resin. The reaction mixture was kept in a constant temperature bath of 50 C. The hydration was followed gas chromatographically (Hexlett- Packard Model 571 (A) to completion by the disappearance of the 2-methoxy-3,4-dihydropyran peak. The reaction was carried out for about 2 to 2 1/2 hours. The reaction was cooled to room temperature (about 25 C) and the reaction product filtered. A slightly yellow liquid was obtained. The yield was about 98 percent. EXAMPLES 2 TO 4 -The procedure described in Example 1 was exactly repeated except that the molar ratio of water to 2-methoxy-3,4-dihydropyran was varied in Examples 2 to 4 as follows: 1.0/1.2; 1.0/2.0 and 1.0/5.6. After the reaction was complete, portions of the reaction products were stored in an oven set at a temperature of 60 C for 27 days of thermal aging 25 percent solu tions of the aged samples in water were prepared and their UV absorbance (at 233 nm) were measured in a 0.1 mm silica cell (vs. air). (Becknan ACTA Model M VIII). The absorbences of the reaction product before and after thermal aging are listed in Table I. The 233 nm absorbence indicates the formation of undesirable aldol type condensation products. TABLE I UV Absorbance Mnle Ratio of 1 H2O/MDPÚ When Made Unheated After 27 days Example H20/MDP When Made Unheated ar 60 C Z. increase 2 1.2 0.751 1.001 33 3 2.0 0.454 0.650 43 4 5.6 0.347 1.414 307 MDP - 2-methoxy-3,4-dihydropyran The data in Table I show that as the ratio of water to 2-methoxy-3,4-dihydropyran increases the solutions are less thermally stable. Examples 5 to 7 These Examples demonstrate the rapid generation of glutaraldehyde when the reaction products produced by the hydration of 2-methoxy-2,4-dihydropyran are added to water at room temperature (about 25 C). The reac tion products were prepared as described in Example 1 with the mole ratio of water to 2-methoxy-3,4-dihydro pyran in Examples 5 to 7 as follows: 1.0/1.0; 1.5/1.0 and 2,0/1.0. Within five minutes after addition to water, gas chromatograph analyses was used to show the gener ation of the glutaraldehyde. These. aqueous solutions were prepared to contain equivalent amounts of 2 methoxy-3,4-dihydropyran. TABLE II Concentration of solution of the Mole Ratio of Glutaraldehyde Examples hydration rroduct (n 1 H2O/MSP2when made found (P: 5 132 1.0/1.0 67.2 6 136 1.5/1.0 73.3 7 150 2.0/1.0 80.0 1 - ppm - parts per'million 2 - HDP - 2-methoxy-3.4-dihydrcpyran Examples 8 to 10 These Examples demonstrate the heat stability of the reaction product produced by the hydration of 2-methoxy-3,4-dihydropyran prepared as in Example 1. The mole ratio of water to 2-methoxy-3,4-dihydropyran in Examples 8 to 10 was as follows: 1.2/1.0; 1.5/1.0 and 2.0/1.0. The reaction products were thermally aged for the time periods and at the temperatures shown in Table III. After thermally aging, the reaction products were added to water to reflect an equivalent initial pyran concentration, Gas chromatograph anal ysis was used to show the concentration of glutaral dehyde. The untreated sample was also analyzed. Control A is a 50 percent glutaraldehyde solution. The results are shown in Table III. TABLE III Glutarldchyde Mole Ratio of After 9 days After 27 days Exa: le H20/MDVlhtnen Made Lt-eate at 600C at 60cc 8 1.2/1.0 74.2 73.3 73.5 9 1.5/1.0 75.1 72.2 76.0 10 2.011.0 79.4 80.0 81.0 10 Control A 50% glutaral- 97.5 92.0 86.6 dehyde solu tion 1 MDP - 2-neroxy-3,4-dihydropyran The data intlable III show that the reaction product of this invention is more thermally stable than. the 50 percent aqueous glutaraldehyde solution. Examples :11 to 14 These Examples demonstrate that the rapid generation of glutaraldehyde from the 2-hydroxy-6-meth oxytetrahydropyran reaction product make this product a very effective microbiocide. The products were prepared by the procedure described in Example 1. The mole ratio of water to 2-methoxy-3,4-dihydropyran in Examples 11 to 14 was as follows: 1.0/1.0; 1.2/1.0; 1.5/1.0 and 2.0/1.0. The concentration of reaction products required to kill all the staphylococus aureus Q107 colony forming units/milliliter) present with 2 hours contact time using a solution having a pH of 7 are shown In Table V, TABLE IV Mole Ratio of Concentration of reaction pro Example H20/MDP1Wben Made duct required (ppmê as made 11 1.0 66 12 1.2 68 13 1.5 70 14 2.0 75 1 - MDP - 2-methoxy-3,4-dihydropyran 2 - ppm 7e parts per million Example 15 The procedure described in Example 1 was exactly repeated except that the amounts of materials used were as follows: 28.5g of 2-methoxy-3,4-dihydropyran, 5.4g of distilled water and 6.6g of catalyst. Also, the reaction was carried cut at a temperature of 35 C instead of 50 C. The reaction was complete in about 2 hours. Example 16 The procedure in Example 1 was exactly repeated except that the amounts of materials used were as follows: 28.5 g of 2-methoxy-3,4-dihydropyran and 4.5 g of distilled water. Also 1.0 g of Nafion-511, (0.95 milliequivalents per gram, supplied by E. I. DuPont de Nemours & Co.) was used instead of the.Rexyn 10 catalyst. The reaction was complete in about 40 minutes. Example 17 The procedure in Example 1 was exactly repeated except that the amounts of materials used were as follows: 28.5g of 2-methoxy-3,4-dihydropyran and 5.4g of distilled water. Also, 0.5g of an 85 percent phosphoric acid solution was used at the catalyst instead of Rexyn 101. The reaction was carried out at a temperature of 90"C instead of 50"C. The reaction was complete in about 90 minutes. The reaction product as ccoled to room tcrperature (ahout 25to) and adjusted to a pH of 7 with 0.36 g of sodium bicarbonate. The reaction product was filtered to remove a small amount of precipitate. Example 18 The procedure of Example 17 was exactly repeated except that 1.0 g of the phosphoric acid solution was used. Also, the reaction was carried out at a te...perature of 65"C. The reaction was complete in about 2 to 2 1/2 hours. The reaction product was cooled to room temperature (about 25"C) and adjusted to a pH of 7 with 0.72 g of sodium bicarbonate. The reaction product was filtered to remove a small amount of precipitate.

Claims: NHAT IS CLAIMED IS: 1. A process for'producing a glutaraldehyde precursor which comprises hydrating 2-alkoxy-3,4-dihydropyran in the presence of an acid catalyst at a temperature of from about 30 to about 100"C, wherein the ratio of water to 2-alkoxy-3,4-dihydropyran is from about 1:1 to about 3:1 and wherein the alkoxy group contains from 1 to 3 carbon atoms. 2. A process as defined in claim 1 wherein the 2-alkoxy-3,4-dihydropyran is 2-methoxy-3,4-dihydropyran. 3 An essentially nonaqueous product comprising 2-hydroxy-6-methoxytetrahydropyran, 2,6-dimethoxytetra hydropyran, glutaraldehyde, and isomers thereof. 4 An essentially nonaqueous product comprising 2-hydroxy-6-methoxytetrahydropyran and 2,6-dimethoxytetrahydropyran. 5. 2-hydroxy-6-methoxytetrahydropyran. 6. A process for producing an aqueous solu tion of glutaraldehyde which comprises adding the reaction product of claim 1 to water. 7. A process for producing an aqueous solution of glutaraldehyde which comprises adding 2 hydroxy-6-methoxytetrahydropyran tc water.

Inventors: CHU, NAN SHIEH
Applicants: UNION CARBIDE CORPORATION
Application year: 1982
Main classification: C07C47
IPC codes: C07C45, A01N35, C07D309, C07C47, C07C67