Method for synthesizing microporous crystalline material

The invention provides a method for synthesizing a porous inorganic solid comprising the steps of: (a) forming a reaction mixture containing water, an alumina source, a silica source, an alkali metal oxide source, and a diquaternary ammonium salt having the formula: ##STR1## wherein R is a diamondoid group, n is from about 1 to about 50, and X is an anion which is not detrimental to the formation of said porous inorganic solid; and PA1 (b) recovering a porous inorganic solid from said reaction mixture.

FIELD OF THE INVENTION 
This invention relates to the synthesis of inorganic porous solids. More 
specifically, this invention provides a method for synthesizing 
crystalline microporous materials which requires no added nucleating seeds 
in the reaction mixture. 
BACKGROUND OF THE INVENTION 
Porous inorganic solids have found great utility as catalysts and 
separations media for industrial application. The openness of their 
microstructure allows molecules access to the relatively large surface 
areas of these materials that enhance their catalytic and sorptive 
activity. The porous materials in use today can be sorted into three broad 
categories using the details of their microstructure as a basis for 
classification. These categories are the amorphous and paracrystalline 
supports, the crystalline molecular sieves and modified layered materials. 
The detailed differences in the microstructures of these materials 
manifest themselves as important differences in the catalytic and sorptive 
behavior of the materials, as well as in differences in various observable 
properties used to characterize them, such as their surface area, the 
sizes of pores and the variability in those sizes, the presence or absence 
of X-ray diffraction patterns and the details in such patterns, and the 
appearance of the materials when their microstructure is studied by 
transmission electron microscopy and electron diffraction methods. 
Amorphous and paracrystalline materials represent an important class of 
porous inorganic solids that have been used for many years in industrial 
applications. Typical examples of these materials are the amorphous 
silicas commonly used in catalyst formulations and the paracrystalline 
transitional aluminas used as solid acid catalysts and petroleum reforming 
catalyst supports. The term "amorphous" is used here to indicate a 
material with no long range order and can be somewhat misleading, since 
almost all materials are ordered to some degree, at least on the local 
scale. An alternate term that has been used to describe these materials is 
"X-ray indifferent". The microstructure of the silicas consists of 100-250 
Angstrom particles of dense amorphous silica (Kirk-Othmer Encyclopedia of 
Chemical Technology, 3rd Edition, Vol. 20, John Wiley & Sons, New York, p. 
766-781, 1982), with the porosity resulting from voids between the 
particles. Since there is no long range order in these materials, the 
pores tend to be distributed over a rather large range. This lack of order 
also manifests itself in the X-ray diffraction pattern, which is usually 
featureless. 
Paracrystalline materials such as the transitional aluminas also have a 
wide distribution of pore sizes, but better defined X-ray diffraction 
patterns usually consisting of a few broad peaks. The microstructure of 
these materials consists of tiny crystalline regions of condensed alumina 
phases and the porosity of the materials results from irregular voids 
between these regions (K. Wefers and Chanakya Misra, "Oxides and 
Hydroxides of Aluminum", Technical Paper No. 19 Revised, Alcoa Research 
Laboratories, p. 54-59, 1987). Since, in the case of either material, 
there is no long range order controlling the sizes of pores in the 
material, the variability in pore size is typically quite high. The sizes 
of pores in these materials fall into a regime called the mesoporous 
range, which, for the purposes of this application, is from about 13 to 
200 Angstroms. 
In sharp contrast to these structurally ill-defined solids are materials 
whose pore size distribution is very narrow because it is controlled by 
the precisely repeating crystalline nature of the materials' 
microstructure. These materials are called "molecular sieves", the most 
important examples of which are zeolites. 
Zeolites, both natural and synthetic, have been demonstrated in the past to 
have catalytic properties for various types of hydrocarbon conversion. 
Certain zeolitic materials are ordered, porous crystalline 
aluminosilicates having a definite crystalline structure as determined by 
X-ray diffraction, within which there are a large number of smaller 
cavities which may be interconnected by a number of still smaller channels 
or pores. These cavities and pores are uniform in size within a specific 
zeolitic material. Since the dimensions of these pores are such as to 
accept for adsorption molecules of certain dimensions while rejecting 
those of larger dimensions, these materials are known as "molecular 
sieves" and are utilized in a variety of ways to take advantage of these 
properties. 
Such molecular sieves, both natural and synthetic, include a wide variety 
of positive ion-containing crystalline silicates. These silicates can be 
described as a rigid three-dimensional framework of SiO.sub.4 and Periodic 
Table Group IIIB element oxide, e.g. Al0 .sub.4, in which the tetrahedra 
are cross-linked by the sharing of oxygen atoms whereby the ratio of the 
total Group IIIB element, e.g. aluminum, and Group IVB element, e.g. 
silicon, atoms to oxygen atoms is 1:2. The electrovalence of the 
tetrahedra containing the Group IIIB element, e.g. aluminum, is balanced 
by the inclusion in the crystal of a cation, for example, an alkali metal 
or an alkaline earth metal cation. 
This can be expressed wherein the ratio of the Group IIIB element, e.g. 
aluminum, to the number of various cations, such as Ca/2, Sr/2, Na, K or 
Li, is equal to unity. One type of cation may be exchanged either entirely 
or partially with another type of cation utilizing ion exchange techniques 
in a conventional manner. By means of such cation exchange, it has been 
possible to vary the properties of a given silicate by suitable selection 
of the cation. The spaces between the tetrahedra are occupied by molecules 
of water prior to dehydration. 
Prior art techniques have resulted in the formation of a great variety of 
synthetic zeolites. Many of these zeolites have come to be designated by 
letter or other convenient symbols, as illustrated by zeolite A (U.S. Pat. 
No. 2,882,243); zeolite X (U.S. Pat. No. 2,882,244); zeolite Y (U.S. Pat. 
No. 3,130,007); zeolite ZK-5 (U.S. Pat. No. 3,247,195); zeolite ZK-4 (U.S. 
Pat. No. 3,314,752); zeolite ZSM-5 (U.S. Pat. No. 3,702,886); zeolite 
ZSM-11 (U.S. Pat. No. 3,709,979); zeolite ZSM-12 (U.S. Pat. No. 
3,832,449); zeolite ZSM-20 (U.S. Pat. No. 3,972,983); ZSM-35 (U.S. Pat. 
No. 4,016,245); and zeolite ZSM-23 (U.S. Pat. No. 4,076,842), merely to 
name a few. 
The SiO.sub.2 /Al.sub.2 0.sub.3 ratio of a given zeolite is often variable. 
For example, zeolite X can be synthesized with SiO.sub.2 /Al.sub.2 0.sub.3 
ratios of from 2 to 3; zeolite Y, from 3 to about 6. In some zeolites, the 
upper limit of the SiO.sub.2 /Al.sub.2 0.sub.3 ratio is unbounded. ZSM-5 
is one such example wherein the SiO.sub.2 /Al.sub.2 0.sub.3 ratio is at 
least 5 and up to the limits of present analytical measurement techniques. 
U.S. Pat. No. 3,941,871 (Re. 29,948) discloses a porous crystalline 
silicate made from a reaction mixture containing no deliberately added 
alumina in the recipe and exhibiting the X-ray diffraction pattern 
characteristic of ZSM-5. U.S. Pat. Nos. 4,061,724; 4,073,865 and 4,104,294 
describe crystalline silicate of varying alumina and metal content. 
Aluminum phosphates are taught in U.S. Pat. Nos. 4,310,440 and 4,385,994, 
for example. These aluminum phosphate materials have essentially 
electroneutral lattices. U.S. Pat. No. 3,801,704 teaches an aluminum 
phosphate treated in a certain way to impart acidity. 
An early reference to a hydrated aluminum phosphate which is crystalline 
until heated at about 110.degree. C., at which point it becomes amorphous 
or transforms, is the "H.sub.1 " phase or hydrate of aluminum phosphate of 
F.d'Yvoire, Memoir Presented to the Chemical Society, No. 392, "Study of 
Aluminum Phosphate and Trivalent Iron", Jul. 6, 1961 (received), pp. 
1762-1776. This material, when crystalline, is identified by the JCPDS 
International Center for Diffraction Data card number 15-274. Once heated 
at about 110.degree. C., however, the d'Yvoire material becomes amorphous 
or transforms to the aluminophosphate form of tridymite. 
Compositions comprising crystals having a framework topology after heating 
at 110.degree. C. or higher giving an X-ray diffraction pattern consistent 
with a material having pore windows formed by 18 tetrahedral members of 
about 12-13 Angstroms in diameter are taught in U.S. Pat. No. 4,880,611. 
A naturally occurring, highly hydrated basic ferric oxyphosphate mineral, 
cacoxenite, is reported by Moore and Shen, Nature, Vol. 306, No. 5941, pp. 
356-358 (1983) to have a framework structure containing very large 
channels with a calculated free pore diameter of 14.2 Angstroms. R. 
Szostak et al., Zeolites: Facts, Figures, Future, Elsevier Science 
Publishers B.V., 1989, present work showing cacoxenite as being very 
hydrophilic, i.e. adsorbing non-polar hydrocarbons only with great 
difficulty. Their work also shows that thermal treatment of cacoxenite 
causes an overall decline in X-ray peak intensity. 
Silicoaluminophosphates of various structures are taught in U.S. Pat. No. 
4,440,871. Aluminosilicates containing phosphorous, i.e. 
silicoaluminophosphates of particular structures are taught in U.S. Pat. 
Nos. 3,355,246 (i.e. ZK-21) and 3,791,964 (i.e. ZK-22). Other teachings of 
silicoaluminophosphates and their synthesis include U.S. Pat. Nos. 
4,673,559 (two-phase synthesis method); 4,623,527 (MCM-10); 4,639,358 
(MCM-1); 4,647,442 (MCM-2); 4,664,897 (MCM-4); 4,638,357 (MCM-5); and 
4,632,811 (MCM-3). 
A method for synthesizing crystalline metalloaluminophosphates is shown in 
U.S. Pat. Nos. 4,713,227, and an antimonophosphoaluminate and the method 
for its synthesis are taught in U.S. Pat. No. 4,619,818. U.S. Pat. No. 
4,567,029 teaches metalloaluminophosphates, and titaniumaluminophosphate 
and the method for its synthesis are taught in U.S. Pat. No. 4,500,651. 
The phosphorus-substituted zeolites of Canadian Patents 911,416; 911,417; 
and 911,418 are referred to as "aluminosilicophosphate" zeolites. Some of 
the phosphorus therein appears to be occluded, not structural. 
U.S. Pat. No. 4,363,748 describes a combination of silica and 
aluminum-calcium-cerium phosphate as a low acid activity catalyst for 
oxidative dehydrogenation. Great Britain Patent 2,068,253 discloses a 
combination of silica and aluminum-calcium-tungsten phosphate as a low 
acid activity catalyst for oxidative dehydrogenation. U.S. Pat. No. 
4,228,036 teaches an alumina-aluminum phosphate-silica matrix as an 
amorphous body to be mixed with zeolite for use as cracking catalyst. U.S. 
Pat. No. 3,213,035 teaches improving hardness of aluminosilicate catalysts 
by treatment with phosphoric acid. The catalysts are amorphous. 
Other patents teaching aluminum phosphates include U.S. Pat. Nos. 
4,365,095; 4,361,705; 4,222,896; 4,210,560; 4,179,358; 4,158,621; 
4,071,471; 4,014,945; 3,904,550; and 3,697,550. 
The precise crystalline microstructure of most zeolites manifests itself in 
a well-defined X-ray diffraction pattern that usually contains many sharp 
maxima and that serves to uniquely define the material. Similarly, the 
dimensions of pores in these materials are very regular, due to the 
precise repetition of the crystalline microstructure. All molecular sieves 
discovered to date have pore sizes in the microporous range, which is 
usually quoted as 2 to 20 Angstroms, with the largest reported being about 
12 Angstroms. 
Certain layered materials, which contain layers capable of being spaced 
apart with a swelling agent, may be pillared to provide materials having a 
large degree of porosity. Examples of such layered materials include 
clays. Such clays may be swollen with water, whereby the layers of the 
clay are spaced apart by water molecules. Other layered materials are not 
swellable with water, but may be swollen with certain organic swelling 
agents such as amines and quaternary ammonium compounds. Examples of such 
non-water swellable layered materials are described in U.S. Pat. No. 
4,859,648 and include layered silicates, magadiite, kenyaite, trititanates 
and perovskites. Another example of a non-water swellable layered 
material, which can be swollen with certain organic swelling agents, is a 
vacancy-containing titanometallate material, as described in U.S. Pat. No. 
4,831,006. 
Once a layered material is swollen, the material may be pillared by 
interposing a thermally stable substance, such as silica, between the 
spaced apart layers. The aforementioned U.S. Pat. Nos. 4,831,006 and 
4,859,648 describe methods for pillaring the non-water swellable layered 
materials described therein and are incorporated herein by reference for 
definition of pillaring and pillared materials. 
Other patents teaching pillaring of layered materials and the pillared 
products include U.S. Pat. Nos. 4,216,188; 4,248,739; 4,176,090; and 
4,367,163; and European Patent Application 205,711. 
The X-ray diffraction patterns of pillared layered materials can vary 
considerably, depending on the degree that swelling and pillaring disrupt 
the otherwise usually well-ordered layered microstructure. The regularity 
of the microstructure in some pillared layered materials is so badly 
disrupted that only one peak in the low angle region on the X-ray 
diffraction pattern is observed, as a d-spacing corresponding to the 
interlayer repeat in the pillared material. Less disrupted materials may 
show several peaks in this region that are generally orders of this 
fundamental repeat. X-ray reflections from the crystalline structure of 
the layers are also sometimes observed. The pore size distribution in 
these pillared layered materials is narrower than those in amorphous and 
paracrystalline materials but broader than that in crystalline framework 
materials. 
The synthetic porous inorganic materials are generally produced from a 
reaction mixture (or "gel") which contains the precursors of the synthetic 
material. Because the necessary seed crystals may be unavailable 
(particularly when the porous inorganic material is new and has not 
previously been synthesized) it would be desirable to provide a synthesis 
method which generates a selected porous inorganic material from a 
particular reaction mixture containing no nucleating seeds. 
The reaction mixture for a particular porous inorganic material may also 
contain an organic directing agent or templating agent. The terms 
"templating agent" and "directing agent" are both used to describe 
compounds (usually organics) added to the reaction mixture to promote 
formation of the desired porous inorganic solid. 
Bulky organic bases which are favored as directing agents include 
cetyltrimetylammonium (CTMA), myristyltrimethylammonium (C.sub.14 TMA), 
decyltrimethylammonium, cetyltrimethylphosphonium, 
octadecyltrimethylphosphonium, benzyltrimethylammonium, cetylpyridinium, 
dodecyltrimethylammonium, and dimethyldidodecylammonium, merely to name a 
few. The templating action of various organic entitles is also discussed 
in A. Dyer An Introduction to Zeolite Molecular Sieves 60 (1988), as well 
as in B. M. Lok et al., The Role of Organic Molecules in Molecular Sieve 
Synthesis 3 Zeolites 282 (1983), which are incorporated by reference as if 
set forth at length herein. These materials are costly, and usually 
account for most of the materials-related expense in the synthesis of 
inorganic porous solids. 
U.S. Pat. No. 4,665,110 to Zones teaches a process for preparing molecular 
sieves using an adamantane-derived template. U.S. Pat. No. 4,826,667 to 
Zones teaches a method for making zeolite SSZ-25 using an adamantane 
quaternary ammonium ion as a template. 
U.S. Pat. No. 4,657,748 to Vaughan and Strohmaier discloses the zeolite 
ECR-1. For a discussion of a proposed structure of zeolite ECR-1, see M. 
E. Leonowicz and D. E. W. Vaughan, "Proposed synthetic zeolite ECR-1 
structure gives a new zeolite framework topology", Nature, Vol. 329, No. 
6142, pages 819-821 (Oct., 1987). 
Adamantane, tricyclo-[3.3.1.1..sup.3,7 ]decane, is a polycyclic alkane with 
the structure of three fused cyclohexane rings. The ten carbon atoms which 
define the framework structure of adamantane are arranged in an 
essentially strainless manner. Four of these carbon atoms, the bridgehead 
carbons, are tetrahedrally disposed about the center of the molecule. The 
other six (methylene carbons) are octahedrally disposed. U.S. Pat. Nos. 
5,019,660 to Chapman and Whitehurst and 5,053,434 to Chapman teach 
diamondoid compounds which bond through the methylene positions of various 
diamondoid compounds, including adamantane. For a survey of the chemistry 
of diamondoid molecules, see Adamantane, The Chemistry of Diamond 
Molecules, Raymond C. Fort, Marcel Dekker, New York, 1976. 
Adamantane has been found to be a useful building block in the synthesis of 
a broad range of organic compounds. 
Many hydrocarbonaceous mineral streams contain some small proportion of 
diamondoid compounds. These high boiling, saturated, three-dimensional 
polycyclic organics are illustrated by adamantane, diamantane, triamantane 
and various side chain substituted homologues, particularly the methyl 
derivatives. These compounds have high melting points and high vapor 
pressures for their molecular weights and have recently been found to 
cause problems during production and refining of hydrocarbonaceous 
minerals, particularly natural gas, by condensing out and solidifying, 
thereby clogging pipes and other pieces of equipment. 
In recent times, new sources of hydrocarbon minerals have been brought into 
production which, for some unknown reason, have substantially larger 
concentrations of diamondoid compounds. Whereas in the past, the amount of 
diamondoid compounds has been too small to cause operational problems such 
as production cooler plugging, now these compounds represent both a larger 
problem and a larger opportunity. The presence of diamondoid compounds in 
natural gas has been found to cause plugging in the process equipment 
requiring costly maintenance downtime to remove. On the other hand, these 
very compounds which can deleteriously affect the profitability of natural 
gas production are themselves valuable products. 
The problem of deposition and plugging by solid diamondoids in natural gas 
production equipment has been successfully addressed by a controlled 
solvent injection process. U.S. Pat. No. 4,952,748 to Alexander and Knight 
teaches the process for extracting diamondoid compounds from a hydrocarbon 
gas stream by contacting the diamondoid-laden hydrocarbon gas with a 
suitable solvent to preferentially dissolve the diamondoid compounds into 
the solvent. U.S. Pat. No. 5,120,899 to Chen and Wentzek teaches a 
particularly useful method for sorbing and isolating diamondoid fractions. 
Further studies have revealed that separation of the diamondoid compounds 
from the diamondoid-enriched solvent is complicated by the fact that 
numerous diamondoid compounds boil in a narrow range of temperatures 
surrounding the boiling range of the most preferred solvents. U.S. Pat. 
Nos. 4,952,747, 4,952,749, and 4,982,049 to Alexander et al. teach various 
methods of concentrating diamondoid compounds in the solvent for, among 
other reasons, recycling the lean solvent fraction for reuse. Each of 
these processes produces an enriched solvent stream containing a mixture 
of diamondoid compounds. 
The above-listed U.S. Patents are incorporated by reference as if set forth 
at length herein for the details of recovering and concentrating 
diamondoid compounds. 
Thus it would be beneficial to (a) provide an economical directing agent; 
(b) convert a now abundant supply of diamondoids into valuable fine 
chemicals; and (c) provide a method for synthesizing porous inorganic 
compounds in the absence of nucleating seeds. 
SUMMARY OF THE INVENTION 
The present invention is directed to an improved method for synthesis of a 
porous inorganic solid comprising forming a reaction mixture containing 
water, an alumina source, a silica source, an alkali metal oxide source, 
and a diquaternary ammonium salt having the formula 
##STR2## 
wherein R is a diamondoid group and n is from about 1 to about 50, 
preferably from about 1 to about 20, more preferably from about 2 to about 
12, most preferably from about 3 to about 10, and wherein X is an anion 
which is not detrimental to the formation of the porous inorganic solid, 
and is preferably a halogen or hydroxide, more preferably I.sup.-. R 
preferably comprises one member of the group consisting of adamantane, 
diamantane, and triamantane, and more preferably comprises adamantane. 
Reaction temperature may range from below ambient to about 400.degree. C., 
and temperatures of from about 120.degree. to about 180.degree. C. are 
preferred for crystallization of the zeolite ECR-1. 
In one embodiment, the reaction mixture is further characterized by the 
following approximate molar ratios of oxides: 
______________________________________ 
SiO.sub.2 /Al.sub.2 O.sub.3: 
10 to 80 
OH.sup.- /SiO.sub.2: 0.50 (fixed) 
H.sub.2 O/SiO.sub.2: 30 to 90 
R/SiO.sub.2: 0.05 to 0.10 
Na.sup.+ /SiO.sub.2 : 
0.54 (fixed) 
______________________________________ 
The synthesis method of the invention functions with or without added 
nucleating seeds. In a preferred embodiment, the reaction mixture of the 
invention contains no nucleating seeds. The porous inorganic solid 
synthesized in accordance with the invention is preferably a crytalline 
microporous material. 
The term "diamondoid" is used in its usual sense, i.e., to designate the 
family of polycyclic alkanes exemplified by adamantane, diamantane, and 
triamantane and their substituted and functionalized homologs. 
The invention further includes a method for the quaternization of 
diamondoid-substituted tertiary amino groups comprising the steps of 
dissolving the diamondoid-substituted tertiary amine in dimethylformamide, 
adding anhydrous sodium carbonate to said dimethylformamide solution, and 
adding excess methyl iodide to the sodium carbonate-containing 
dimethylformamide mixture. 
The new templates and the specific conditions using these templates as 
disclosed herein facilitate the crystallization of ECR-1 as well as other 
unidimensional large pore zeolites. These templates by no means resemble 
those used in U.S. Pat. No. 4,657,748 for the formation of ECR-1, and the 
discovery that they nucleate the crystallization of ECR-1 is unexpected. 
In addition, no nucleating seed was required using these templates to 
produce ECR-1. In the ECR-1 synthesis set forth in U.S. Pat. No. 
4,657,748, the template used was a bis-(2-hydroxyalky) dimethylammonium 
chloride. In addition, sodium zeolite (aluminosilicate) nucleating seeds 
were required for the crystallization. In the synthesis of the present 
invention, the crystallization proceeds without adding sodium zeolite 
seeds. Further, the ECR-1 samples synthesized in accordance with the 
present invention showed useful catalytic activity as evidenced by the 
observed high Alpha values. 
When Alpha Value is examined, it is noted that the Alpha Value is an 
approximate indication of the catalytic cracking activity of the catalyst 
compared to a standard catalyst and it gives the relative rate constant 
(rate of normal hexane conversion per volume of catalyst per unit time). 
It is based on the activity of silica-alumina cracking catalyst taken as 
an Alpha of 1 (Rate Constant=0.016 sec.sup.-1). The Alpha Test is 
described in U.S. Pat. No. 3,354,078; in the Journal of Catalysis, Vol. 4, 
p. 527 (1965); Vol. 6, p. 278 (1966); and Vol. 61, p. 395 (1980), each 
incorporated herein by reference as to that description. The experimental 
conditions of the test used herein include a constant temperature of 
538.degree. C. and a variable flow rate as described in detail in the 
Journal of Catalysis, vol. 61, p. 395. 
The synthesis process of the invention hydrothermally produces ECR-1 
crystals at a SiO.sub.2 /Al.sub.2 0.sub.3 feed ration of 10-40, and at 
temperatures between 120.degree.-160.degree. C. At a SiO.sub.2 /Al.sub.2 
0.sub.3 ratio of about 10, the ECR-1 product formed has a SiO.sub.2 
/Al.sub.2 0.sub.3 ratio of 7.5, and can contain minor amounts of Analcime. 
At a SiO.sub.2 /Al.sub.2 0.sub.3 feed ratio of about 40, the zeolite 
product has a SiO.sub.2 /Al.sub.2 0.sub.3 ratio of about 15 and contains a 
mixture of ECR-1 and mordenite. At a SiO.sub.2 /Al.sub.2 0.sub.3 feed 
ratio of about 80, the zeolite product has a SiO.sub.2 /Al.sub.2 0.sub.3 
ratio of about 30 and contains essentially mordenite. The synthesis method 
of the invention produces essentially pure ECR-1 product using a SiO.sub.2 
/Al.sub.2 0.sub.3 feed ratio of from about 10 to about 20. The 
as-synthesized zeolites are stable to calcination at 538.degree. C. in 
nitrogen followed by calcination in air. 
In accordance with the present invention, ECR-1 can be synthesized 
hydrothermally using the above adamantane-containing diquarternary 
ammonium iodides (where n is from about 6 to about 9) as templates. The 
preferred aluminum source is NaA10.sub.2, while the preferred silicon 
source is SiO.sub.2 sol (30% SiO.sub.2 in H.sub.2 0), which is 
commercially available as Catalog No. SX0140-1 from EM Science, Inc. 
Embodiments Synthesis of the Directing Agent 
The directing agent of the present invention may suitably be synthesized in 
accordance with the following general procedure which includes the 
sequential steps of: (1) imine formation between 2-adamantanone and a 
primary amine, (2) hydrogenation of the imine to the secondary amine, (3) 
methylation to the tertiary amine and (4) quaternization with methyl 
iodide. The overall yield to the tertiary amine is typically 90% or 
higher. By combining steps (1) and (2) and carrying out a reductive 
amination, the synthesis can start with a secondary amine and produce a 
tertiary amine directly and with similar high yield. Although the 
quaternization of adamantyl substituted tertiary amines requires more 
drastic conditions than the usual mild conditions employed in 
quaternizations, it typically produces 90% or higher yields from the 
tertiary amines in HPLC grade dimethylformamide in a pressure vessel. By 
this route, the directing agent synthesis of the invention has produced a 
variety of novel adamantane-containing amines and quaternary ammonium 
salts of different sizes, shapes, and charge densities. These quaternary 
ammonium salts are useful as nucleating agents for syntheses of zeolites 
and other porous catalysts, as well as for pharmeceutical applications as 
antivirals. 
The directing agent may be synthesized in accordance with the following 
procedure: 
(1) Imine formation between 2-adamantanone and a primary amine: the imine 
formation was carried out in an appropriate solvent which formed an 
azeotrope with water to displace the following equilibrium to the right: 
EQU 2-Ad.dbd.O+RNH.sub.2 .rarw..fwdarw.2- Ad.dbd.NR+H.sub.2 0 
The reaction was carried out in a flask equipped with a mechanical stirrer, 
a Dean-Stark trap, and a condenser. In general, the reaction was complete 
in about four hours as evidenced by the calculated amount of water 
collected in the Dean-Stark trap. When there were more than one primary 
amino group present in the reactant amine, toluene was used as the solvent 
because these amines typically had high boiling points. To ensure all the 
amino groups were to be reacted, a 10% mole excess 2-adamantanone was 
employed. After the reaction the toluene was distilled off and the excess 
2-adamantanone was removed by sublimation under vacuum. In cases where the 
amines contained only one primary amino group and were relatively low 
boiling, cyclohexane was used as the solvent to azeotrope out the produced 
water, and the amine was used in 20% mole excess. The pot temperature was 
kept below the boiling point of the amine to prevent the amine from 
distilling off. After reaction was complete, both cyclohexane and the 
excess amine were removed by distillation. The structures of the imine 
products were established by C-13 NMR. The yield based on the reactant not 
in excess was generally near quantitative. 
(2) Hydrogenation of Imines to Secondary Amines: The hydrogenation was 
carried out in ethanol using Pd/C as the catalyst at 50.degree. C. or 
Ni/Kieselgel as the catalyst at 100.degree. C. Complete hydrogenation took 
48-72 hours. The hydrogenated products were generally crystalline or 
crystallizable from ethanol. The structures of the secondary amines were 
confirmed by C-13 NMR. The yield from the imine was generally 
quantitative. 
(3) Methylation of Secondary to Tertiary Amine: The methylation step was 
carried out in accordance with the following general procedure. For a 
discussion of methylation, see H. W. Geluk and V. G. Keiser, Org. 
Synthesis, 53, 8, 1973. One mole of a secondary amino group (in these 
Examples, a molecule often contained more than one secondary amino group) 
was added slowly to 2.5 moles formic acid (96% in water) in a 2-neck flask 
equipped with an air-driven mechanical stirrer and a water condenser. Upon 
stirring, 1.1 moles of formaldehyde (37% in water) were added slowly, 
followed by the addition of 100 ml water. The mixture was slowly heated to 
reflux. The solid amine went into solution and gas (CO.sub.2) was evolved. 
The mixture was refluxed overnight until the gas evolution had ceased. 
Upon cooling, an amount of 195 ml concentrated HCl (36%) was added slowly 
and the excess formaldehyde and formic acid were driven off at boiling 
with mechanical stirring while bubbling through a stream of nitrogen. The 
mixture was cooled down and neutralized with 25 % sodium hydroxide 
solution. The tertiary amine formed was then extracted with ether. The 
ether extract was washed with water and dried over anhydrous magnesium 
sulfate. After filtration the ether was distilled off to recover the 
tertiary amine product. The structure of the product was characterized by 
C-13 NMR. Yield in this methylation step averaged 90%. 
(4) Quaternization: Quaternization of tertiary amino groups, without an 
adamantyl substituent, required mild conditions under which the adamantyl 
substituted amino groups are not affected, and was achieved by slowly 
dropping methyl iodide into an ethanol solution of the amine keeping the 
temperature under 35.degree. C. The product precipitated out as a solid. 
The quaternization of adamantyl substituted tertiary amino groups required 
more stringent conditions. The presence of any protonic compound either as 
a solvent or as an impurity resulted in the formation of proton ammonium 
instead of quaternary ammonium salts. The best solvent was discovered to 
be HPLC grade (pure) dimethylformamide which was syringed directly into 
the quaternization reactor to avoid possible exposure to moisture. It was 
also found to be advantageous to add to the reaction a small amount of 
anhydrous sodium carbonate. Excess methyl iodide, at a mole ratio of 1.5 
CH.sub.3 I to 1 amino group and an elevated temperature 
(60.degree.-90.degree. C.) were required. Due to the low boiling point of 
CH.sub.3 I, the reactions were carried out in a Parr reactor. The yield of 
the quaternization was as high as 90%; however, in some cases other parts 
of the molecule could degrade (see the following Examples II and III) 
rendering the overall yield significantly lower.