Caustic washed molecular sieves

A novel improved molecular sieve is prepared by a caustic wash process. The sieves so prepared show improved properties in reactions involving e.g., superior acid scavenging ability.

This invention relates to a novel product, caustic-washed molecular sieves, 
and to the caustic wash process to prepare them. 
The molecular sieves which are used in this process are alumino-silicate 
zeolites. Generally speaking, naturally-occurring zeolites can be defined 
as a group of crystalline solids, hydrated alumino-silicates of mono- and 
divalent bases, which are capable of losing part or all of their water 
without change of lattice framework, adsorbing other compounds in place of 
the water removed, and which are capable of undergoing base exchange. A 
synthetic zeolite, on the other hand, is synthesized from a combination of 
basic oxides (AlO.sub.2, SiO.sub.2, Na.sub.2 O, K.sub.2 O, etc.) in an 
aqueous system to yield a hydrated or semi-hydrated crystalline structure. 
Following heat treatment, the zeolites are characterized and classified 
primarily by X-ray powder diffraction methods. Although there is lack of a 
systematic chemical method for naming synthetic, complex 
alumino-silicates, historically each new synthetic zeolite is assigned an 
arbitrary letter or group of letters and numbers. The meaning of these 
arbitrary symbols is well understood by those skilled in the art. 
It has been found that synthetic zeolites of the A class can be improved by 
a caustic wash process of this invention. This class has a pore size in 
the range of from about 3 to about 5 A. 
A-type molecular sieves are readily commercially available, and have a 
regular crystal structure and uniform pore size. The most commonly 
available sieves, Types 3A and 4A, are all operable in the invention. 
These sieves have the following properties: 
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Type Formula Pore Diameter 
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3A K.sub.q Na.sub.12-q [(AlO.sub.2).sub.12 (SiO.sub.2).sub.12 ] . 
27H.sub.2 O 3A 
4A Na.sub.12 [(AlO.sub.2).sub.12 (SiO.sub.2).sub.12 ] . 27H.sub.2 
4A 
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The caustic wash process involves the following procedure: the molecular 
sieves are slurried with a large volume of appropriate dilute caustic, 
such as aqueous 0.10-0.5N sodium hydroxide for the 4A sieve and potassium 
hydroxide for the 3A sieve. The mixture is heated for from 15 minutes to 1 
hour at 70.degree.-100.degree. C. while stirring with water until the pH 
of the wash water is between 10-11. The filter cake is broken up, and 
dried at a sufficient temperature and time to reduce ignition loss (as 
determined using standard procedures) to between 2-8%. 
The caustic washed sieves so produced have improved properties in terms of 
yield and kinetics, when used in various chemical processes, such as those 
described in Weinstock, South Africa Pat. No. 74/7635, issued Nov. 3, 
1976, and Weinstock et al., Tet. Letters, "The Chemistry of Cephamycins, 
IV, Acylation of Amides in the Presence of Neutral Acid Scavengers.

One illustrative preparation of the caustic washed sieves is as follows: 
Experimental Method for Caustic Washing Sieves 
1. Weigh 10 gms. of molecular sieves, Linde type 4A, into a 500 ml. 
Erlenmeyer flask. 
2. Add 200 ml. of 0.18N sodium hydroxide to the flask. 
3. Heat slurry to 70.degree.-100.degree. C. for 1/4 hour while stirring 
(magnetic stirrer). 
4. Filter hot slurry rapidly through medium sintered glass funnel. 
5. Wash filter cake repeatedly with cold water, until wash solution is pH 
10-11. Do not overwash. 
6. Suck the filter cake completely dry. 
7. Break up filter cake thoroughly. Place wet sieves in porcelain crucible. 
8. Place crucible in a 300.degree. C. preheated muffle furnace. Dry for 2 
hours. 
9. Cool crucible in dessicator using dry sieves (&lt; 3% H.sub.2 O) as 
dessicant. 
10. Obtain loss on ignition (L.O.I.) on cooled sieves. Value should be 
2-8%. If necessary, adjust drying times or temperature to obtain this 
range. 
11. Store sieves in tightly capped bottle. 
The effect of caustic washing is to remove surface contaminants through 
dissolution which can be observed in scanning electron micrographs. 
The caustic-washed sieves so prepared can be used to prepare e.g., sodium 
7-(2-thienylacetamido)-7-methoxy-3-carbamoyloxymethyl-3-cephem-4-carboxyla 
te. One illustrative procedure is as follows: 
A mixture of 2.76 g. (4 mmoles) of the dimethoxymethyl ester of 
7.beta.-(D-5-tosylamino-5-carboxyvaleramido)-3-carbamoyloxymethyl-7.alpha. 
-methoxy-3-cephem-4-carboxylate, 3 g. of dry Linde-type 4A molecular 
sieves, having 2-8% water, 2 ml. of thienylacetyl chloride (16 mmoles) in 
34 ml. of dichloroethane is stirred at reflux for 5 hours t-Butanol, 0.38 
ml. (4 mmoles) is then added and stirring continued for 2 hours. At the 
end of this period, another 0.095 ml. (1 mmole) of t-butanol is introduced 
and the reaction mixture was stirred for another 1/2 hour. The reaction 
mixture is cooled to 0.degree.-5.degree. C. in an ice-water bath. The 
molecular sieves are removed by suction-filtration and then washed with 40 
ml. of ice-cold methanol. The filtrate and wash were combined and cooled 
to 0.degree. C. An ice-cold solution of 8.3 ml. concentrated HCl and 9.5 
ml. MeOH is added and the solution warmed to 15.degree. C. and stirred at 
15.degree. C. for 2 hrs. 40 min. When the hydrolysis is complete the 
reaction is quenched by adding to a suspension of 22 g. sodium bicarbonate 
in 120 ml. of water at 0.degree.-5.degree. C. The two-phase solution is 
stirred for 10 min. The heavy salt deposit that forms is removed by 
filtration and washed with a small amount of 5% NaCl solution containing 
0.5% sodium bicarbonate. The dichloroethane layer is separated and 
extracted with 2 .times. 20 ml. of a solution of 0.5% NaHCO.sub.3 + 5% 
NaCl. The aqueous fractions are combined and washed with 20 ml. of 
dichloroethane. The bicarbonate solution was assayed by liquid 
chromatography to contain 73% sodium 
7-(2-thienylacetamido)-7-methoxy-3-carbamoyloxymethyl-3-cephem-4-carboxyla 
te and 2.1% of the unchanged starting material. 
Following this or a similar procedure, caustic-washed and unwashed sieves 
were evaluated. The unwashed sieves yielded about 65% total product after 
about 21/2 hours reaction time, after which this yield decreased rapidly. 
By contrast, the washed sieves yielded 70% total product at 3 hours 
reaction time, and 75% at 4 hours, all yields measured by liquid 
chromatography methods.