U.S. patent application number 12/275117 was filed with the patent office on 2009-05-21 for organosilanes and substrates covalently bonded with same and methods for synthesis and use.
This patent application is currently assigned to Dionex Corporation. Invention is credited to Xiaodong Liu, Christopher A. Pohl.
Application Number | 20090130767 12/275117 |
Document ID | / |
Family ID | 36295524 |
Filed Date | 2009-05-21 |
United States Patent
Application |
20090130767 |
Kind Code |
A1 |
Liu; Xiaodong ; et
al. |
May 21, 2009 |
ORGANOSILANES AND SUBSTRATES COVALENTLY BONDED WITH SAME AND
METHODS FOR SYNTHESIS AND USE
Abstract
The present invention provides novel silicon compounds, methods
for making these novel silicon compounds, compositions comprising
these novel silicon compounds attached to substrates, methods for
attaching the novel silicon compounds to substrates and methods for
using the compositions in a variety of chromatographic
applications.
Inventors: |
Liu; Xiaodong; (Cupertino,
CA) ; Pohl; Christopher A.; (Union City, CA) |
Correspondence
Address: |
MORGAN, LEWIS & BOCKIUS, LLP
ONE MARKET SPEAR STREET TOWER
SAN FRANCISCO
CA
94105
US
|
Assignee: |
Dionex Corporation
Sunnyvale
CA
|
Family ID: |
36295524 |
Appl. No.: |
12/275117 |
Filed: |
November 20, 2008 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
11059179 |
Feb 15, 2005 |
7468130 |
|
|
12275117 |
|
|
|
|
Current U.S.
Class: |
436/72 ;
210/198.2; 210/656; 252/184; 556/419; 556/422 |
Current CPC
Class: |
B01J 20/286 20130101;
B01J 20/3257 20130101; C07B 2200/11 20130101; C07F 7/1804 20130101;
B01J 20/3259 20130101; B01J 20/3261 20130101; B01J 20/287
20130101 |
Class at
Publication: |
436/72 ; 556/419;
556/422; 210/656; 210/198.2; 252/184 |
International
Class: |
G01N 33/00 20060101
G01N033/00; C07F 7/10 20060101 C07F007/10; C07F 7/08 20060101
C07F007/08; C09K 3/00 20060101 C09K003/00; B01D 15/08 20060101
B01D015/08 |
Claims
1. A composition comprising a compound of structural Formula (II):
##STR00014## or salts, solvates or hydrates thereof wherein:
R.sup.1, R.sup.2 and R.sup.3 are independently alkyl, alkoxy,
alkoxycarbonyl, alkylsulfonyloxy, amino, aryl, aryloxycarbonyl,
arylsulfonyloxy, halo or hydroxyl, optionally substituted with one
or more R.sup.14 groups, provided that at least one of R.sup.1,
R.sup.2 and R.sup.3 are not alkyl, aryl or hydroxyl; L.sub.1 is
alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl; Y is
--C(O)N(R.sup.4)(R.sup.5), --N(R.sup.4)C(O)R.sup.7,
--N(R.sup.4)S(O.sub.2)R.sup.7, --S(O).sub.2N(R.sup.4)(R.sup.5),
--OC(O)R.sup.7, --OC(O)N(R.sup.4)(R.sup.5),
--N(R.sup.4)C(O)OR.sup.7, --N(R.sup.4)C(O)N(R.sup.5)(R.sup.6) or
--N(R.sup.4)S(O.sub.2)N(R.sup.5)(R.sup.6); and R.sup.4, R.sup.5 and
R.sup.6 are independently hydrogen, (C.sub.1-C.sub.6)alkyl
optionally substituted with one or more hydroxy or cyano groups or
(C.sub.5-C.sub.7)aryl optionally substituted with one or more
hydroxy or cyano groups; R.sup.7 is (C.sub.1-C.sub.6)alkyl
optionally substituted with one or more hydroxy or cyano groups or
(C.sub.5-C.sub.7)aryl optionally substituted with one or more
hydroxy or cyano groups and R.sup.14 is (C.sub.1-C.sub.6)alkyl;
provided that one of R.sup.4, R.sup.5 or R.sup.6 is not hydrogen;
wherein said compound is covalently bonded to a substrate.
2. The composition of claim 1 in which said compound of structural
Formula (II) is selected from the group consisting of:
##STR00015##
3. The composition of claim 1 in which the compound is covalently
bonded to the substrate by reaction of one or more of R.sup.1,
R.sup.2 and R.sup.3 with reactive groups on the substrate selected
from the group consisting of silanol, alkoxysilane, halosilane or
aminosilane.
4. The composition of claim 1 in which
--SiR.sup.1(R.sup.2)(R.sup.3) is covalently bonded to another
compound of claim 1 by reaction with reactive groups selected from
the group consisting of silanol, alkoxysilane or halosilane on the
other compound.
5. The composition of claim 4 of structural Formula (III):
##STR00016##
6. The composition of claim 5 having a structure selected from the
group consisting of: ##STR00017##
7. A chromatographic method comprising flowing an aqueous liquid
through a bed of separation medium comprising a compound of
structural Formula (II): ##STR00018## or salts, solvates or
hydrates thereof wherein: R.sup.1, R.sup.2 and R.sup.3 are
independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy,
amino, aryl, aryloxycarbonyl, arylsulfonyloxy, halo or hydroxyl,
optionally substituted with one or more R.sup.14 groups, provided
that at least one of R.sup.1, R.sup.2 and R.sup.3 are not alkyl,
aryl or hydroxyl; L.sub.1 is alkyldiyl, heteroalkyldiyl, aryldiyl
or heteroaryldiyl; Y is --C(O)N(R.sup.4)(R.sup.5),
--N(R.sup.4)C(O)R.sup.7, --N(R.sup.4)S(O.sub.2)R.sup.7,
--S(O).sub.2N(R.sup.4)(R.sup.5), --OC(O)R.sup.7,
--OC(O)N(R.sup.4)(R.sup.5), --N(R.sup.4)C(O)OR.sup.7,
--N(R.sup.4)C(O)N(R.sup.5)(R.sup.6) or
--N(R.sup.4)S(O.sub.2)N(R.sup.5)(R.sup.6); and R.sup.4, R.sup.5 and
R.sup.6 are independently hydrogen, (C.sub.1-C.sub.6)alkyl
optionally substituted with one or more hydroxy or cyano groups or
(C.sub.5-C.sub.7)aryl optionally substituted with one or more
hydroxy or cyano groups; R.sup.7 is (C.sub.1-C.sub.6)alkyl
optionally substituted with one or more hydroxy or cyano groups or
(C.sub.5-C.sub.7)aryl optionally substituted with one or more
hydroxy or cyano groups and R.sup.14 is (C.sub.1-C.sub.6)alkyl;
provided that one of R.sup.4, R.sup.5 or R.sup.6 is not hydrogen;
wherein said compound is covalently bonded to a substrate.
8. A chromatographic method comprising flowing an aqueous liquid
through a bed of separation medium comprising a compound of
structural Formula (II): ##STR00019## or salts, solvates or
hydrates thereof, wherein R.sup.1, R.sup.2 and R.sup.3 are
independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy,
amino, aryl, aryloxycarbonyl, arylsulfonyloxy, halo or hydroxyl,
optionally substituted with one or more (C.sub.1-C.sub.6)alkyl
groups, provided that at least one of R.sup.1, R.sup.2 and R.sup.3
is not alkyl, aryl or hydroxyl; L.sub.1 is alkyldiyl,
heteroalkyldiyl, aryldiyl or heteroaryldiyl; and Y is
--C(O)N(R.sup.4)(R.sup.5), --N(R.sup.4)C(O)R.sup.7,
--N(R.sup.4)S(O.sub.2)R.sup.7, --S(O).sub.2N(R.sup.4)(R.sup.5),
--OC(O)R.sup.7, --OC(O)N(R.sup.4)(R.sup.5),
--N(R.sup.4)C(O)OR.sup.7, --N(R.sup.4)C(O)N(R.sup.5)(R.sup.6) or
--N(R.sup.4)S(O.sub.2)N(R.sup.5)(R.sup.6), wherein R.sup.4, R.sup.5
and R.sup.6 are independently hydrogen, (C.sub.1-C.sub.6)alkyl
optionally substituted with one or more hydroxy or cyano groups or
(C.sub.5-C.sub.7)aryl optionally substituted with one or more
hydroxy or cyano groups, provided that at least one of R.sup.4,
R.sup.5 and R.sup.6 is not hydrogen; and R.sup.7 is
(C.sub.1-C.sub.6)alkyl optionally substituted with one or more
hydroxy or cyano groups or (C.sub.5-C.sub.7)aryl optionally
substituted with one or more hydroxy or cyano groups; wherein said
compound is covalently bonded to a substrate, said composition
further comprising a compound of structural Formula (IV) covalently
bonded to said substrate: ##STR00020## wherein R.sup.8, R.sup.9,
and R.sup.10 are independently alkyl, alkoxy, alkoxycarbonyl,
alkylsulfonyloxy, amino aryl, aryloxycarbonyl, aryloxy,
arylsulfonyloxy, halo or hydroxyl optionally substituted with one
or more independently selected (C.sub.1-C.sub.6)alkyl groups,
provided that at least one of R.sup.1, R.sup.2 and R.sup.3 is not
alkyl, aryl or hydroxyl; L.sub.2 is alkyldiyl, heteroalkyldiyl,
aryldiyl or heteroaryldiyl; and W is an ionizable group and
different than Y.
9. A method for the chromatographic separation of analytes in a
liquid sample comprising flowing the liquid sample through medium
comprising a compound of structural Formula (II): ##STR00021## or
salts, solvates or hydrates thereof wherein: R.sup.1, R.sup.2 and
R.sup.3 are independently alkyl, alkoxy, alkoxycarbonyl,
alkylsulfonyloxy, amino, aryl, aryloxycarbonyl, arylsulfonyloxy,
halo or hydroxyl, optionally substituted with one or more R.sup.14
groups, provided that at least one of R.sup.1, R.sup.2 and R.sup.3
are not alkyl, aryl or hydroxyl; L.sub.1 is alkyldiyl,
heteroalkyldiyl, aryldiyl or heteroaryldiyl; Y is
--C(O)N(R.sup.4)(R.sup.5), --N(R.sup.4)C(O)R.sup.7,
--N(R.sup.4)S(O.sub.2)R.sup.7, --S(O).sub.2N(R.sup.4)(R.sup.5),
--OC(O)R.sup.7, --OC(O)N(R.sup.4)(R.sup.5),
--N(R.sup.4)C(O)OR.sup.7, --N(R.sup.4)C(O)N(R.sup.5)(R.sup.6) or
--N(R.sup.4)S(O.sub.2)N(R.sup.5)(R.sup.6); and R.sup.4, R.sup.5 and
R.sup.6 are independently hydrogen, (C.sub.1-C.sub.6)alkyl
optionally substituted with one or more hydroxy or cyano groups or
(C.sub.5-C.sub.7)aryl optionally substituted with one or more
hydroxy or cyano groups; R.sup.7 is (C.sub.1-C.sub.6)alkyl
optionally substituted with one or more hydroxy or cyano groups or
(C.sub.5-C.sub.7)aryl optionally substituted with one or more
hydroxy or cyano groups and R.sup.14 is (C.sub.1-C.sub.6)alkyl;
provided that one of R.sup.4, R.sup.5 or R.sup.6 is not hydrogen;
wherein said compound is covalently bonded to a substrate.
10. A method for the chromatographic separation of analytes in a
liquid sample comprising flowing the liquid sample through medium
comprising a compound of structural Formula (II): ##STR00022## or
salts, solvates or hydrates thereof, wherein R.sup.1, R.sup.2 and
R.sup.3 are independently alkyl, alkoxy, alkoxycarbonyl,
alkylsulfonyloxy, amino, aryl, aryloxycarbonyl, arylsulfonyloxy,
halo or hydroxyl, optionally substituted with one or more
(C.sub.1-C.sub.6)alkyl groups, provided that at least one of
R.sup.1, R.sup.2 and R.sup.3 is not alkyl, aryl or hydroxyl;
L.sub.1 is alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl;
and Y is --C(O)N(R.sup.4)(R.sup.5), --N(R.sup.4)C(O)R.sup.7,
--N(R.sup.4)S(O.sub.2)R.sup.7, --S(O).sub.2N(R.sup.4)(R.sup.5),
--OC(O)R.sup.7, --OC(O)N(R.sup.4)(R.sup.5),
--N(R.sup.4)C(O)OR.sup.7, --N(R.sup.4)C(O)N(R.sup.5)(R.sup.6) or
--N(R.sup.4)S(O.sub.2)N(R.sup.5)(R.sup.6), wherein R.sup.4, R.sup.5
and R.sup.6 are independently hydrogen, (C.sub.1-C.sub.6)alkyl
optionally substituted with one or more hydroxy or cyano groups or
(C.sub.5-C.sub.7)aryl optionally substituted with one or more
hydroxy or cyano groups, provided that at least one of R.sup.4,
R.sup.5 and R.sup.6 is not hydrogen; and R.sup.7 is
(C.sub.1-C.sub.6)alkyl optionally substituted with one or more
hydroxy or cyano groups or (C.sub.5-C.sub.7)aryl optionally
substituted with one or more hydroxy or cyano groups; wherein said
compound is covalently bonded to a substrate, said composition
further comprising a compound of structural Formula (IV) covalently
bonded to said substrate: ##STR00023## wherein R.sup.8, R.sup.9,
and R.sup.10 are independently alkyl, alkoxy, alkoxycarbonyl,
alkylsulfonyloxy, amino aryl, aryloxycarbonyl, aryloxy,
arylsulfonyloxy, halo or hydroxyl optionally substituted with one
or more independently selected (C.sub.1-C.sub.6)alkyl groups,
provided that at least one of R.sup.1, R.sup.2 and R.sup.3 is not
alkyl, aryl or hydroxyl; L.sub.2 is alkyldiyl, heteroalkyldiyl,
aryldiyl or heteroaryldiyl; and W is an ionizable group and
different than Y.
11. A method for simultaneous analysis of cationic, neutral and
anionic surfactants in a liquid sample comprising flowing the
liquid sample through medium comprising the composition of a
compound of structural Formula (II): ##STR00024## or salts,
solvates or hydrates thereof, wherein R.sup.1, R.sup.2 and R.sup.3
are independently alkyl, alkoxy, alkoxycarbonyl, alkylsulfonyloxy,
amino, aryl, aryloxycarbonyl, arylsulfonyloxy, halo or hydroxyl,
optionally substituted with one or more (C.sub.1-C.sub.6)alkyl
groups, provided that at least one of R.sup.1, R.sup.2 and R.sup.3
is not alkyl, aryl or hydroxyl; L.sub.1 is alkyldiyl,
heteroalkyldiyl, aryldiyl or heteroaryldiyl; and Y is
--C(O)N(R.sup.4)(R.sup.5), --N(R.sup.4)C(O)R.sup.7,
--N(R.sup.4)S(O.sub.2)R.sup.7, --S(O).sub.2N(R.sup.4)(R.sup.5),
--OC(O)R.sup.7, --OC(O)N(R.sup.4)(R.sup.5),
--N(R.sup.4)C(O)OR.sup.7, --N(R.sup.4)C(O)N(R.sup.5)(R.sup.6) or
--N(R.sup.4)S(O.sub.2)N(R.sup.5)(R.sup.6), wherein R.sup.4, R.sup.5
and R.sup.6 are independently hydrogen, (C.sub.1-C.sub.6)alkyl
optionally substituted with one or more hydroxy or cyano groups or
(C.sub.5-C.sub.7)aryl optionally substituted with one or more
hydroxy or cyano groups, provided that at least one of R.sup.4,
R.sup.5 and R.sup.6 is not hydrogen; and R.sup.7 is
(C.sub.1-C.sub.6)alkyl optionally substituted with one or more
hydroxy or cyano groups or (C.sub.5-C.sub.7)aryl optionally
substituted with one or more hydroxy or cyano groups; wherein said
compound is covalently bonded to a substrate, said composition
further comprising a compound of structural Formula (IV) covalently
bonded to said substrate: ##STR00025## wherein R.sup.8, R.sup.9,
and R.sup.10 are independently alkyl, alkoxy, alkoxycarbonyl,
alkylsulfonyloxy, amino aryl, aryloxycarbonyl, aryloxy,
arylsulfonyloxy, halo or hydroxyl optionally substituted with one
or more independently selected (C.sub.1-C.sub.6)alkyl groups,
provided that at least one of R.sup.1, R.sup.2 and R.sup.3 is not
alkyl, aryl or hydroxyl; L.sub.2 is alkyldiyl, heteroalkyldiyl,
aryldiyl or heteroaryldiyl; and W is an ionizable group and
different than Y.
12. A chromatography column comprising the composition of claim 1
packed in a suitable housing.
13. A packing comprising the compound of claim 1 covalently bonded
to a first substrate and a compound of structural Formula (IV)
bonded to a second substrate wherein Formula (IV) is: ##STR00026##
R.sup.8, R.sup.9, and R.sup.10 are independently alkyl, alkoxy,
alkoxycarbonyl, alkylsulfonyloxy, amino aryl, aryloxycarbonyl,
aryloxy, arylsulfonyloxy, halo or hydroxyl, optionally substituted
with one or more of the same or different R.sup.13 groups, provided
that at least one of R.sup.1, R.sup.2 and R.sup.3 are not alkyl,
aryl or hydroxyl; R.sup.13 is (C.sub.1-C.sub.6)alkyl; L.sub.2 is
alkyldiyl, heteroalkyldiyl, aryldiyl or heteroaryldiyl; and W is an
ionizable group.
14. The compound of claim 13, in which the first substrate and the
second substrate are a silica substrate.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a divisional application of pending U.S.
application Ser. No. 11/059,179 filed on Feb. 15, 2005.
1. FIELD
[0002] The present invention relates generally to novel silicon
compounds, methods for making these novel silicon compounds,
compositions comprising these novel silicon compounds attached to
substrates, methods for attaching the novel silicon compounds to
substrates and methods for using the compositions in a variety of
chromatographic applications.
2. BACKGROUND
[0003] Conventional reversed phase silica columns (e.g., ODS) are
widely used as general-purpose stationary phases for
chromatographic separations (Neue, "HPLC Columns--Theory,
Technology, and Practice," WILEY-VCH, New York, 1997, 183-203).
However, some drawbacks, including, for example, "phase collapse"
(i.e., dewetting) in highly aqueous environments, weak retention of
ionic compounds and residual silanol activity which leads to peak
tailing of basic analytes prevent employment of conventional
reverse phase silica columns in certain applications.
[0004] Polar-embedded phases improve the peak shape of basic
analytes and enable operation of reverse phase HPLC columns in
highly aqueous environments (O'Gara et al., LC-GC 2001, 19
(6):632-641). Commonly used polar groups include, for example,
amides, ureas, ethers and carbamates. In general, polar-embedded
phases provide superior peak shapes of basic analytes and are more
compatible with highly aqueous environments when compared to
general purpose reverse phases. Further, polar embedded phases
often have selectivities which are substantially different from
those exhibited by conventional C-18 packings.
[0005] Surfactants are important components of a variety of
consumer, industrial, agricultural and pharmaceutical products.
Surfactant analysis is often complicated by the presence of
mixtures which are difficult to resolve using conventional
chromatography. Surfactants have been analyzed by liquid
chromatography on reversed-phase columns (e.g., C18, C8, cyano,
phenyl, etc.), normal phase columns, ion-exchange columns and
size-exclusion columns (Schmitt, "Analysis of Surfactants,"
2.sup.nd edition, Marcel Dekker, Inc, New York, 2001, 197-292). C18
columns provide reasonable separation, peak efficiency and
asymmetry, especially for anionic surfactants. However, the
presence of underivatized silanols on silica-based reversed-phase
columns often prevents satisfactory resolution of cationic
surfactants. For example, C18 reversed phase columns fail to
separate individual oligomers of polyethylene glycol (PEG) based
surfactants. In addition, because of "de-wetting" caused by
necessary usage of high aqueous mobile phases, conventional
high-density C18 columns are unsuitable for analysis of highly
hydrophilic hydrotopes, (e.g. sodium naphthalene sulfonate and
xylene sulfonate). Despite the availability of a variety of HPLC
columns to analyze a wide range of surfactants using a plurality of
different conditions, no single column can be used to separate
cationic, nonionic, and anionic surfactants in a single run using
simple and volatile, mass spectroscopy compatible, mobile
phases.
[0006] Accordingly, what is needed are novel silane compounds which
have both hydrophobic and polar functionality, substrates
functionalized with these new silane compounds and the use of these
novel functionalized substrates to simultaneously separate
cationic, nonionic and anionic surfactants.
3. SUMMARY
[0007] The present invention satisfies these and other needs by
providing a new class of silane compounds, which have hydrophobic
and polar functionality, substrates functionalized with these new
silane compounds and the use of these novel functionalized
substrates to simultaneously separate cationic, nonionic, and
anionic surfactants.
[0008] In one aspect, a compound described by Formula (I) is
disclosed:
##STR00001##
or salts, solvates or hydrates thereof. The compound of Formula (I)
has at least one activated silyl group (e.g., Si(OMe).sub.3,
--SiMe(OMe).sub.2, --SiMe.sub.2(OMe), --Si(OEt).sub.3,
--SiMe(OEt).sub.2, --SiMe.sub.2(OEt), --SiMe.sub.2NMe.sub.2,
--SiCl.sub.3, etc.), at least one polar group (e.g., amide,
sulfonamide, carbamate, urea, ester, etc.) and a short head chain
(e.g., (C.sub.1-C.sub.6) alkyl) connected to the polar group.
[0009] In another aspect, a compound of structural Formula (II) is
provided:
##STR00002##
[0010] or salts, solvates or hydrates thereof
[0011] wherein:
[0012] R.sup.1, R.sup.2 and R.sup.3 are independently alkyl,
alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino, aryl,
aryloxycarbonyl, arylsulfonyloxy, halo or hydroxyl, optionally
substituted with one or more R.sup.12 groups, provided that at
least one of R.sup.1, R.sup.2 and R.sup.3 are not alkyl, aryl or
hydroxyl;
[0013] L.sub.1 is alkyldiyl, heteroalkyldiyl, aryldiyl or
heteroaryldiyl;
[0014] Y is --C(O)N(R.sup.4)(R.sup.5), --N(R.sup.4)C(O)R.sup.7,
--N(R.sup.4)S(O.sub.2)R.sup.7, --S(O).sub.2N(R.sup.4)(R.sup.5),
--OC(O)R.sup.7, --OC(O)N(R.sup.4)(R.sup.5),
--N(R.sup.4)C(O)OR.sup.7, --N(R.sup.4)C(O)N(R.sup.5)(R.sup.6) or
--N(R.sup.4)S(O.sub.2)N(R.sup.5)(R.sup.6); and
[0015] R.sup.4, R.sup.5 and R.sup.6 are independently hydrogen,
(C.sub.1-C.sub.6)alkyl optionally substituted with one or more
hydroxy or cyano groups or (C.sub.5-C.sub.7)aryl optionally
substituted with one or more hydroxy or cyano groups;
[0016] R.sup.7 is (C.sub.1-C.sub.6)alkyl optionally substituted
with one or more hydroxy or cyano groups or (C.sub.5-C.sub.7)aryl
optionally substituted with one or more hydroxy or cyano groups;
and
[0017] R.sup.14 is (C.sub.1-C.sub.6)alkyl;
[0018] provided that one of R.sup.4, R.sup.5 or R.sup.6 is not
hydrogen.
[0019] In another aspect, a composition including a compound of
Formula (II) covalently bonded to a substrate is provided. In some
embodiments, the composition is in a flow-through bed suitable for
use a reverse phase chromatographic medium.
[0020] In still another aspect, a composition comprising the
compound of structural Formula (II) covalently bonded to a
substrate and a compound of structural Formula (IV) covalently
bonded to the substrate is provided wherein:
##STR00003##
[0021] R.sup.8, R.sup.9, and R.sup.10 are independently alkyl,
alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino aryl,
aryloxycarbonyl, aryloxy, arylsulfonyloxy, halo or hydroxyl
optionally substituted with one or more of the same or different
R.sup.14 groups, provided that at least one of R.sup.1, R.sup.2 and
R.sup.3 are not alkyl, aryl or hydroxyl;
[0022] R.sup.15 is (C.sub.1-C.sub.6)alkyl;
[0023] L.sub.2 is alkyldiyl, heteroalkyldiyl, aryldiyl or
heteroaryldiyl; and
[0024] W is an ionizable group.
[0025] In still another aspect, a chromatographic method is
provided. An aqueous liquid is flowed through a bed of separation
medium, which includes either a composition containing a compound
of Formula (II) covalently bonded to a substrate or a composition
comprising the compound of structural Formula (II) covalently
bonded to a substrate and a compound of structural Formula (IV)
covalently bonded to the substrate.
[0026] In still another aspect, a method for chromatographic
separation of analytes in a liquid sample is provided. The liquid
sample is flowed through medium, which includes a composition
containing a compound of Formula (II) covalently bonded to a
substrate or a composition comprising the compound of structural
Formula (II) covalently bonded to a substrate and a compound of
structural Formula (IV) covalently bonded to the substrate.
[0027] In still another aspect, a method for simultaneous analysis
of inorganic analytes and organic analytes in a liquid sample is
provided. The liquid sample is flowed through medium, which
includes a composition containing a compound of Formula (II)
covalently bonded to a substrate or a composition of a compound of
structural Formula (II) and a compound of structural Formula (IV)
covalently bonded to a substrate.
4. BRIEF DESCRIPTION OF THE DRAWINGS
[0028] FIG. 1 illustrates the synthesis of an amide of Formula
(II);
[0029] FIG. 2 illustrates the synthesis of amine derivatives of
Formula (II);
[0030] FIG. 3 illustrates the synthesis of alcohol derivatives of
Formula (II);
[0031] FIG. 4 illustrates synthesis of a compound of Formula
(IV);
[0032] FIG. 5 illustrates the separation of uracil, p-butyl benzoic
acid and phenanthrene by a C8 column and a column packed with
composition 27;
[0033] FIG. 6 illustrates separation of a number of surfactants
with and a column packed with composition 36;
[0034] FIG. 7 illustrates the separation of Triton X-100 with a
conventional C18 column and a column packed with composition
36;
[0035] FIG. 8 illustrates the separation of a number of surfactants
with a conventional C18 column and a column packed with composition
36;
[0036] FIG. 9 illustrates the separation of lauryldimethylbenzyl
ammonium chloride with a conventional C18 column and a column
packed with composition 36; and
[0037] FIG. 10 illustrates the separation of sodium xylene
sulfonate with a conventional C18 column and a column packed with
composition 36.
5. DETAILED DESCRIPTION
5.1 Definitions
[0038] "Alkyl" by itself or as part of another substituent, refers
to a saturated or unsaturated, branched, straight-chain or cyclic
monovalent hydrocarbon radical derived by the removal of one
hydrogen atom from a single carbon atom of a parent alkane, alkene
or alkyne. Typical alkyl groups include, but are not limited to,
methyl; ethyls such as ethanyl, ethenyl, ethynyl; propyls such as
propan-1-yl, propan-2-yl, cyclopropan-1-yl, prop-1-en-1-yl,
prop-1-en-2-yl, prop-2-en-1-yl(allyl), cycloprop-1-en-1-yl;
cycloprop-2-en-1-yl, prop-1-yn-1-yl, prop-2-yn-1-yl, etc.; butyls
such as butan-1-yl, butan-2-yl, 2-methyl-propan-1-yl,
2-methyl-propan-2-yl, cyclobutan-1-yl, but-1-en-1-yl,
but-1-en-2-yl, 2-methyl-prop-1-en-1-yl, but-2-en-1-yl,
but-2-en-2-yl, buta-1,3-dien-1-yl, buta-1,3-dien-2-yl,
cyclobut-1-en-1-yl, cyclobut-1-en-3-yl, cyclobuta-1,3-dien-1-yl,
but-1-yn-1-yl, but-1-yn-3-yl, but-3-yn-1-yl, etc.; and the
like.
[0039] The term "alkyl" is specifically intended to include groups
having any degree or level of saturation, i.e., groups having
exclusively single carbon-carbon bonds, groups having one or more
double carbon-carbon bonds, groups having one or more triple
carbon-carbon bonds and groups having mixtures of single, double
and triple carbon-carbon bonds. Where a specific level of
saturation is intended, the expressions "alkanyl," "alkenyl," and
"alkynyl" are used. In some embodiments, an alkyl group comprises
from 1 to 20 carbon atoms. In other embodiments, an alkyl group
comprises from 1 to 10 carbon atoms.
[0040] "Alkanyl" by itself or as part of another substituent,
refers to a saturated branched, straight-chain or cyclic alkyl
radical derived by the removal of one hydrogen atom from a single
carbon atom of a parent alkane. Typical alkanyl groups include, but
are not limited to, methanyl; ethanyl; propanyls such as
propan-1-yl, propan-2-yl(isopropyl), cyclopropan-1-yl, etc.;
butanyls such as butan-1-yl, butan-2-yl(sec-butyl),
2-methyl-propan-1-yl(isobutyl), 2-methyl-propan-2-yl (t-butyl),
cyclobutan-1-yl, etc.; and the like.
[0041] "Alkenyl" by itself or as part of another substituent,
refers to an unsaturated branched, straight-chain or cyclic alkyl
radical having at least one carbon-carbon double bond derived by
the removal of one hydrogen atom from a single carbon atom of a
parent alkene. The group may be in either the cis or trans
conformation about the double bond(s). Typical alkenyl groups
include, but are not limited to, ethenyl; propenyls such as
prop-1-en-1-yl, prop-1-en-2-yl, prop-2-en-1-yl(allyl),
prop-2-en-2-yl, cycloprop-1-en-1-yl, cycloprop-2-en-1-yl; butenyls
such as but-1-en-1-yl, but-1-en-2-yl, 2-methyl-prop-1-en-1-yl,
but-2-en-1-yl, but-2-en-1-yl, but-2-en-2-yl, buta-1,3-dien-1-yl,
buta-1,3-dien-2-yl, cyclobut-1-en-1-yl, cyclobut-1-en-3-yl,
cyclobuta-1,3-dien-1-yl, etc.; and the like.
[0042] "Alkynyl" by itself or as part of another substituent,
refers to an unsaturated branched, straight-chain or cyclic alkyl
radical having at least one carbon-carbon triple bond derived by
the removal of one hydrogen atom from a single carbon atom of a
parent alkyne. Typical alkynyl groups include, but are not limited
to, ethynyl; propynyls such as prop-1-yn-1-yl, prop-2-yn-1-yl,
etc.; butynyls such as but-1-yn-1-yl, but-1-yn-3-yl, but-3-yn-1-yl,
etc.; and the like.
[0043] "Alkyldiyl" by itself or as part of another substituent,
refers to a saturated or unsaturated, branched, straight-chain or
cyclic divalent hydrocarbon group derived by the removal of one
hydrogen atom from each of two different carbon atoms of a parent
alkane, alkene or alkyne, or by the removal of two hydrogen atoms
from a single carbon atom of a parent alkane, alkene or alkyne. The
two monovalent radical centers or each valency of the divalent
radical center can form bonds with the same or different atoms.
Typical alkyldiyl groups include, but are not limited to
methandiyl; ethyldiyls such as ethan-1,1-diyl, ethan-1,2-diyl,
ethen-1,1-diyl, ethen-1,2-diyl; propyldiyls such as
propan-1,1-diyl, propan-1,2-diyl, propan-2,2-diyl, propan-1,3-diyl,
cyclopropan-1,1-diyl, cyclopropan-1,2-diyl, prop-1-en-1,1-diyl,
prop-1-en-1,2-diyl, prop-2-en-1,2-diyl, prop-1-en-1,3-diyl,
cycloprop-1-en-1,2-diyl, cycloprop-2-en-1,2-diyl,
cycloprop-2-en-1,1-diyl, prop-1-yn-1,3-diyl, etc.; butyldiyls such
as, butan-1,1-diyl, butan-1,2-diyl, butan-1,3-diyl, butan-1,4-diyl,
butan-2,2-diyl, 2-methyl-propan-1,1-diyl, 2-methyl-propan-1,2-diyl,
cyclobutan-1,1-diyl; cyclobutan-1,2-diyl, cyclobutan-1,3-diyl,
but-1-en-1,1-diyl, but-1-en-1,2-diyl, but-1-en-1,3-diyl,
but-1-en-1,4-diyl, 2-methyl-prop-1-en-1,1-diyl,
2-methanylidene-propan-1,1-diyl, buta-1,3-dien-1,1-diyl,
buta-1,3-dien-1,2-diyl, buta-1,3-dien-1,3-diyl,
buta-1,3-dien-1,4-diyl, cyclobut-1-en-1,2-diyl,
cyclobut-1-en-1,3-diyl, cyclobut-2-en-1,2-diyl,
cyclobuta-1,3-dien-1,2-diyl, cyclobuta-1,3-dien-1,3-diyl,
but-1-yn-1,3-diyl, but-1-yn-1,4-diyl, buta-1,3-diyn-1,4-diyl, etc.;
and the like. Where specific levels of saturation are intended, the
nomenclature alkanyldiyl, alkenyldiyl and/or alkynyldiyl is used.
In some embodiments, the alkyldiyl group is
(C.sub.1-C.sub.20)alkyldiyl. In other embodiments, the alkyldiyl
group is (C.sub.1-C.sub.10)alkyldiyl. In still other embodiments,
the alkyldiyl group is a saturated acyclic alkanyldiyl group in
which the radical centers are at the terminal carbons, e.g.,
methandiyl(methano); ethan-1,2-diyl(ethano); propan-1,3-diyl
(propano); butan-1,4-diyl(butano); and the like (also referred to
as alkyleno, defined infra).
[0044] "Alkyleno" by itself or as part of another substituent,
refers to a straight-chain alkyldiyl group having two terminal
monovalent radical centers derived by the removal of one hydrogen
atom from each of the two terminal carbon atoms of straight-chain
parent alkane, alkene or alkyne. Typical alkyleno groups include,
but are not limited to, methano; ethylenos such as ethano, etheno,
ethyno; propylenos such as propano, prop[1]eno, propa[1,2]dieno,
prop[1]yno, etc.; butylenos such as butano, but[1]eno, but[2]eno,
buta[1,3]dieno, but[1]yno, but[2]yno, but[1,3]diyno, etc.; and the
like. Where specific levels of saturation are intended, the
nomenclature alkano, alkeno and/or alkyno is used. In some
embodiments, the alkyleno group is (C.sub.1-C.sub.20)alkyleno. In
other embodiments, the alkyleno group is (C.sub.1-C.sub.10)
alkyleno. In still other embodiments, the alkyleno group is a
straight-chain saturated alkano groups, e.g., methano, ethano,
propano, butano, and the like.
[0045] "Alkylsulfonyloxy" by itself or as part of another
substituent, refers to a radical --OS(O).sub.2R.sup.30 where
R.sup.30 represents an alkyl or cycloalkyl group as defined
herein.
[0046] "Alkoxy" by itself or as part of another substituent, refers
to a radical --OR.sup.31 where R.sup.31 represents an alkyl or
cycloalkyl group as defined herein Representative examples include,
but are not limited to, methoxy, ethoxy, propoxy, butoxy,
cyclohexyloxy and the like.
[0047] "Alkoxycarbonyl" by itself or as part of another
substituent, refers to a radical --C(O)OR.sup.32 where R.sup.32
represents an alkyl or cycloalkyl group as defined herein.
[0048] "Aryl" by itself or as part of another substituent, refers
to a monovalent aromatic hydrocarbon radical derived by the removal
of one hydrogen atom from a single carbon atom of a parent aromatic
ring system. Typical aryl groups include, but are not limited to,
groups derived from aceanthrylene, acenaphthylene,
acephenanthrylene, anthracene, azulene, benzene, chrysene,
coronene, fluoranthene, fluorene, hexacene, hexaphene, hexylene,
as-indacene, s-indacene, indane, indene, naphthalene, octacene,
octaphene, octalene, ovalene, penta-2,4-diene, pentacene,
pentalene, pentaphene, perylene, phenalene, phenanthrene, picene,
pleiadene, pyrene, pyranthrene, rubicene, triphenylene,
trinaphthalene and the like. In some embodiments, an aryl group
comprises from 5 to 20 carbon atoms. In other embodiments, an aryl
group comprises from 5 to 12 carbon atoms.
[0049] "Aryldiyl" by itself or as part of another substituent
refers to a divalent hydrocarbon radical derived by the removal of
one hydrogen atom from each of two different carbon atoms of a
parent aromatic system or by removal of two hydrogen atoms from a
single carbon atom of a parent aromatic ring system. The two
monovalent radical centers or each valency of the divalent center
can form bonds with the same or different atom(s). Typical aryldiyl
groups include, but are not limited to, groups derived from
aceanthrylene, acenaphthylene, acephenanthrylene, anthracene,
azulene, benzene, chrysene, coronene, fluoranthene, fluorene,
hexacene, hexaphene, hexylene, as-indacene, s-indacene, indane,
indene, naphthalene, octacene, octaphene, octalene, ovalene,
penta-2,4-diene, pentacene, pentalene, pentaphene, perylene,
phenalene, phenanthrene, picene, pleiadene, pyrene, pyranthrene,
rubicene, triphenylene, trinaphthalene and the like. In some
embodiments, an aryldiyl group comprises from 5 to 20 carbon atoms.
In other embodiments, an aryldiyl group comprises from 5 to 12
carbon atoms.
[0050] "Aryloxycarbonyl" by itself or as part of another
substituent, refers to a radical --C(O)OR.sup.33 where R.sup.33
represents an aryl group as defined herein.
[0051] "Arylsulfonyloxy" by itself or as part of another
substituent, refers to a radical --OS(O).sub.2R.sup.35 where
R.sup.35 represents an alkyl or cycloalkyl group as defined
herein.
[0052] "Cycloalkyl" by itself or as part of another substituent,
refers to a saturated or unsaturated cyclic alkyl radical. Where a
specific level of saturation is intended, the nomenclature
"cycloalkanyl" or "cycloalkenyl" is used. Typical cycloalkyl groups
include, but are not limited to, groups derived from cyclopropane,
cyclobutane, cyclopentane, cyclohexane and the like. In some
embodiments, the cycloalkyl group is (C.sub.3-C.sub.10) cycloalkyl.
In other embodiments, the cycloalkyl group is (C.sub.3-C.sub.7)
cycloalkyl.
[0053] "Heteroalkyl, Heteroalkanyl Heteroalkenyl, Heteroalkanyl,
Heteroalkyldiyl and Heteroalkyleno" by themselves or as part of
another substituent, refer to alkyl, alkanyl, alkenyl, alkynyl,
alkyldiyl and alkyleno groups, respectively, in which one or more
of the carbon atoms (and any associated hydrogen atoms) are each
independently replaced with the same or different heteroatomic
groups. Typical heteroatomic groups which can be included in these
groups include, but are not limited to, --O--, --S--, --O--O--,
--S--S--, --O--S--, --NR.sup.35R.sup.36--, .dbd.N--N.dbd.,
--N.dbd.N--, --N.dbd.N--NR.sup.37R.sup.38, --PR.sup.39--,
--P(O).sub.2--, --POR.sup.40--, --O--P(O).sub.2--, --SO--,
--SO.sub.2--, --SnR.sup.41R.sup.42-- and the like, where R.sup.35,
R.sup.36, R.sup.37, R.sup.38, R.sup.39, R.sup.40, R.sup.41 and
R.sup.42 are independently hydrogen, alkyl, substituted alkyl,
aryl, substituted aryl, arylalkyl, substituted arylalkyl,
cycloalkyl, substituted cycloalkyl, cycloheteroalkyl, substituted
cycloheteroalkyl, heteroalkyl, substituted heteroalkyl, heteroaryl,
substituted heteroaryl, heteroarylalkyl or substituted
heteroarylalkyl.
[0054] "Heteroaryl" by itself or as part of another substituent,
refers to a monovalent heteroaromatic radical derived by the
removal of one hydrogen atom from a single atom of a parent
heteroaromatic ring system. Typical heteroaryl groups include, but
are not limited to, groups derived from acridine, arsindole,
carbazole, .beta.-carboline, chromane, chromene, cinnoline, furan,
imidazole, indazole, indole, indoline, indolizine, isobenzofuran,
isochromene, isoindole, isoindoline, isoquinoline, isothiazole,
isoxazole, naphthyridine, oxadiazole, oxazole, perimidine,
phenanthridine, phenanthroline, phenazine, phthalazine, pteridine,
purine, pyran, pyrazine, pyrazole, pyridazine, pyridine,
pyrimidine, pyrrole, pyrrolizine, quinazoline, quinoline,
quinolizine, quinoxaline, tetrazole, thiadiazole, thiazole,
thiophene, triazole, xanthene, and the like. In some embodiments,
the heteroaryl group is from 5-20 membered heteroaryl. In other
embodiments, the heteroaryl group is from 5-10 membered heteroaryl.
In still other embodiments, the heteroaryl groups are those derived
from thiophene, pyrrole, benzothiophene, benzofuran, indole,
pyridine, quinoline, imidazole, oxazole and pyrazine.
[0055] "Heteroaryldiyl" by itself or as part of another substituent
refers to a divalent radical derived by the removal of one hydrogen
atom from each of two different carbon atoms of a parent
heteroaromatic system or by removal of two hydrogen atoms from a
single carbon atom of a parent aromatic ring system. The two
monovalent radical centers or each valency of the divalent center
can form bonds with the same or different atom(s) Typical
heteroaryldiyl groups include, but are not limited to, groups
derived from acridine, arsindole, carbazole, .alpha.-carboline,
chromane, chromene, cinnoline, furan, imidazole, indazole, indole,
indoline, indolizine, isobenzofuran, isochromene, isoindole,
isoindoline, isoquinoline, isothiazole, isoxazole, naphthyridine,
oxadiazole, oxazole, perimidine, phenanthridine, phenanthroline,
phenazine, phthalazine, pteridine, purine, pyran, pyrazine,
pyrazole, pyridazine, pyridine, pyrimidine, pyrrole, pyrrolizine,
quinazoline, quinoline, quinolizine, quinoxaline, tetrazole,
thiadiazole, thiazole, thiophene, triazole, xanthene, and the like.
In some embodiments, a heteroaryldiyl group comprises from 5 to 20
carbon atoms. In other embodiments, a heteroaryldiyl group
comprises from 5 to 12 carbon atoms.
[0056] "Parent Aromatic Ring System" by itself or as part of
another substituent, refers to an unsaturated cyclic or polycyclic
ring system having a conjugated n electron system. Specifically
included within the definition of "parent aromatic ring system" are
fused ring systems in which one or more of the rings are aromatic
and one or more of the rings are saturated or unsaturated, such as,
for example, fluorene, indane, indene, phenalene, etc. Typical
parent aromatic ring systems include, but are not limited to,
aceanthrylene, acenaphthylene, acephenanthrylene, anthracene,
azulene, benzene, chrysene, coronene, fluoranthene, fluorene,
hexacene, hexaphene, hexylene, as-indacene, s-indacene, indane,
indene, naphthalene, octacene, octaphene, octalene, ovalene,
penta-2,4-diene, pentacene, pentalene, pentaphene, perylene,
phenalene, phenanthrene, picene, pleiadene, pyrene, pyranthrene,
rubicene, triphenylene, trinaphthalene and the like.
[0057] "Parent Heteroaromatic Ring System" by itself or as part of
another substituent, refers to a parent aromatic ring system in
which one or more carbon atoms (and any associated hydrogen atoms)
are independently replaced with the same or different heteroatom.
Typical heteroatoms to replace the carbon atoms include, but are
not limited to, N, P, O, S, Si, etc. Specifically included within
the definition of "parent heteroaromatic ring systems" are fused
ring systems in which one or more of the rings are aromatic and one
or more of the rings are saturated or unsaturated, such as, for
example, arsindole, benzodioxan, benzofuran, chromane, chromene,
indole, indoline, xanthene, etc. Typical parent heteroaromatic ring
systems include, but are not limited to, arsindole, carbazole,
.beta.-carboline, chromane, chromene, cinnoline, furan, imidazole,
indazole, indole, indoline, indolizine, isobenzofuran, isochromene,
isoindole, isoindoline, isoquinoline, isothiazole, isoxazole,
naphthyridine, oxadiazole, oxazole, perimidine, phenanthridine,
phenanthroline, phenazine, phthalazine, pteridine, purine, pyran,
pyrazine, pyrazole, pyridazine, pyridine, pyrimidine, pyrrole,
pyrrolizine, quinazoline, quinoline, quinolizine, quinoxaline,
tetrazole, thiadiazole, thiazole, thiophene, triazole, xanthene,
and the like.
[0058] "Substituted" refers to a group in which one or more
hydrogen atoms are independently replaced with the same or
different substituent(s). Typical substituents include, but are not
limited to, -M, --R.sup.60, --O--, .dbd.O, --OR.sup.60,
--SR.sup.60, --S.sup.-, .dbd.S, --NR.sup.60R.sup.61,
.dbd.NR.sup.60, --CF.sub.3, --CN, --OCN, --SCN, --NO, --NO.sub.2,
.dbd.N.sub.2, --N.sub.3, --S(O).sub.2O.sup.-, --S(O).sub.2OH,
--S(O).sub.2R.sup.60, --OS(O.sub.2)O.sup.-, --OS(O).sub.2R.sup.61,
--P(O)(O.sup.-).sub.2, --P(O)(OR.sup.60)(O.sup.-),
--OP(O)(OR.sup.60)(OR.sup.61), --C(O)R.sup.60, --C(S)R.sup.60,
--C(O)OR.sup.60, --C(O)NR.sup.60R.sup.61, --C(O)O.sup.-,
--C(S)OR.sup.60, --NR.sup.62C(O)NR.sup.60R.sup.61,
--NR.sup.62C(S)NR.sup.60R.sup.61,
--NR.sup.62C(NR.sup.63)NR.sup.60R.sup.61 and
--C(NR.sup.62)NR.sup.60R.sup.61 where M is independently a halogen;
R.sup.60, R.sup.61, R.sup.62 and R.sup.63 are independently
hydrogen, alkyl, substituted alkyl, alkoxy, substituted alkoxy,
cycloalkyl, substituted cycloalkyl, cycloheteroalkyl, substituted
cycloheteroalkyl, aryl, substituted aryl, heteroaryl or substituted
heteroaryl, or optionally R.sup.60 and R.sup.61 together with the
nitrogen atom to which they are bonded form a cycloheteroalkyl or
substituted cycloheteroalkyl ring; and R.sup.64 and R.sup.65 are
independently hydrogen, alkyl, substituted alkyl, aryl, cycloalkyl,
substituted cycloalkyl, cycloheteroalkyl, substituted
cycloheteroalkyl, aryl, substituted aryl, heteroaryl or substituted
heteroaryl, or optionally R.sup.64 and R.sup.65 together with the
nitrogen atom to which they are bonded form a cycloheteroalkyl or
substituted cycloheteroalkyl ring. Preferably, substituents include
-M, --R.sup.60, .dbd.O, --OR.sup.60, --SR.sup.60, --S.sup.-,
.dbd.S, --NR.sup.60R.sup.61, .dbd.NR.sup.60, --CF.sub.3, --CN,
--OCN, --SCN, --NO, --NO.sub.2, .dbd.N.sub.2, --N.sub.3,
--S(O).sub.2R.sup.60, --OS(O.sub.2)O.sup.-, --OS(O).sub.2R.sup.60,
--P(O)(O.sup.-).sub.2, --P(O)(OR.sup.60)(O.sup.-),
--OP(O)(OR.sup.60)(OR.sup.61), --C(O)R.sup.60, --C(S)R.sup.60,
--C(O)OR.sup.60, --C(O)NR.sup.60R.sup.61, --C(O)O.sup.-,
--NR.sup.62C(O)NR.sup.60R.sup.61, more preferably, -M, --R.sup.60,
.dbd.O, --OR.sup.60, --SR.sup.60, --NR.sup.60R.sup.61, --CF.sub.3,
--CN, --NO.sub.2, --S(O).sub.2R.sup.60, --P(O)(OR.sup.60)(O.sup.-),
--OP(O)(OR.sup.60)(OR.sup.61), --C(O)R.sup.60, --C(O)OR.sup.60,
--C(O)NR.sup.60R.sup.61, --C(O)O.sup.-, most preferably, -M,
--R.sup.60, .dbd.O, --OR.sup.60, --SR.sup.60, --NR.sup.60R.sup.61,
--CF.sub.3, --CN, --NO.sub.2, --S(O).sub.2R.sup.60,
--OP(O)(OR.sup.60)(OR.sup.61), --C(O)R.sup.60, --C(O)OR.sup.60,
--C(O)O.sup.-, where R.sup.60, R.sup.61 and R.sup.62 are as defined
above.
5.2 Organosilanes and Substrates Thereof
[0059] The present invention provides novel silane compounds which
have both hydrophobic and ionic functionality. At one terminus of
the novel silane compound is a silyl group, which can be covalently
attached to a substrate. At the other end of the novel silane
compound is a short head chain (e.g., (C.sub.1-C.sub.6)alkyl). The
silyl group and the short head chain are connected via a linker
joined to a polar group. The linkers may be alkyl, aryl, heteroaryl
or heteroalkyl groups while the polar group may be amide,
carbamate, urea, sulfonamide, etc.
[0060] In one aspect, a compound described by Formula (I) is
provided
##STR00004##
or salts, solvates or hydrates thereof. Compounds of Formula (I)
have at least one activated silyl group, a head chain joined by a
linker connected to a polar group.
[0061] An "activated silyl group" refers to silicon moieties, which
are capable of reacting with the surface of a substrate to form a
covalent bond with the surface. For example, an activated silyl
group can react with the surface of a silica substrate comprising
surface Si--OH groups to create siloxane bonds between compounds of
Formula (I) and the substrate. Exemplary activated silyl groups
include, but are not limited to, --Si(OMe).sub.3,
--SiMe(OMe).sub.2, --SiMe.sub.2(OMe), --Si(OEt).sub.3,
--SiMe(OEt).sub.2, --SiMe.sub.2(OEt), --SiMe.sub.2NMe.sub.2 and
--SiCl.sub.3. A "linker" refers to an alkyl, heteroalkyl, aryl or
heteroaryl group. A "polar group" refers to an amide, sulfonamide,
carbamate, urea, ester, etc. The linker in compounds of Formula (I)
serve as a spacer between the activated silyl group and the polar
group.
[0062] In some embodiments, a compound of structural Formula (II)
is provided:
##STR00005##
[0063] or salts, solvates or hydrates thereof
[0064] wherein:
[0065] R.sup.1, R.sup.2 and R.sup.3 are independently alkyl,
alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino, aryl,
aryloxycarbonyl, arylsulfonyloxy, halo or hydroxyl, optionally
substituted with one or more R.sup.14 groups, provided that at
least one of R.sup.1, R.sup.2 and R.sup.3 are not alkyl, aryl or
hydroxyl;
[0066] L.sub.1 is alkyldiyl, heteroalkyldiyl, aryldiyl or
heteroaryldiyl;
[0067] Y is --C(O)N(R.sup.4)(R.sup.5), --N(R.sup.4)C(O)R.sup.7,
--N(R.sup.4)S(O.sub.2)R.sup.7, --S(O).sub.2N(R.sup.4)(R.sup.5),
--OC(O)R.sup.7--OC(O)N(R.sup.4)(R.sup.5), --N(R.sup.4)C(O)OR.sup.7,
--N(R.sup.4)C(O)N(R.sup.5)(R.sup.6) or
--N(R.sup.4)S(O.sub.2)N(R.sup.5)(R.sup.6); and
[0068] R.sup.4, R.sup.5 and R.sup.6 are independently hydrogen,
(C.sub.1-C.sub.6)alkyl optionally substituted with one or more
hydroxy or cyano groups or (C.sub.5-C.sub.7)aryl optionally
substituted with one or more hydroxy or cyano groups;
[0069] R.sup.7 is (C.sub.1-C.sub.6)alkyl optionally substituted
with one or more hydroxy or cyano groups or (C.sub.5-C.sub.7)aryl
optionally substituted with one or more hydroxy or cyano groups
and
[0070] R.sup.14 is (C.sub.1-C.sub.6)alkyl;
[0071] provided that one of R.sup.4, R.sup.5 or R.sup.6 is not
hydrogen.
[0072] In some embodiments, R.sup.1, R.sup.2 and R.sup.3 are
independently alkyl, alkoxy or halo. In other embodiments, R.sup.1,
R.sup.2 and R.sup.3 are alkoxy. In still other embodiments,
R.sup.1, R.sup.2 and R.sup.3 are alkyl or alkoxy. In still other
embodiments, R.sup.1, R.sup.2 and R.sup.3 are ethoxy or methyl.
[0073] In some embodiments, L.sub.1 is alkyldiyl. In other
embodiments, L.sub.1 is alkanyldiyl. In still other embodiments,
L.sub.1 is alkyleno. In still other embodiments, L.sub.1 is
(C.sub.6-C.sub.20)alkanyleno. In still other embodiments, L.sub.1
is (C.sub.8-C.sub.15)alkanyleno. In still other embodiments,
L.sub.1 is (C.sub.10-C.sub.11) alkanyleno.
[0074] In some embodiments, R.sup.4, R.sup.5 and R.sup.6 are
independently hydrogen, alkyl, or aryl. In other embodiments,
R.sup.4, R.sup.5 and R.sup.6 are independently alkyl, or aryl. In
still other embodiments, R.sup.4, R.sup.5 and R.sup.6 are
independently methyl or phenyl. In still other embodiments,
R.sup.4, R.sup.5 and R.sup.6 are methyl.
[0075] In some embodiments, R.sup.1, R.sup.2 and R.sup.3 are
independently alkyl, alkoxy or halo, L.sub.1 is alkyldiyl and
R.sup.4, R.sup.5 and R.sup.6 are independently hydrogen, alkyl, or
aryl. In other embodiments, R.sup.1, R.sup.2 and R.sup.3 are alkyl
or alkoxy, L.sub.1 is (C.sub.8-C.sub.15)alkanyleno and R.sup.4,
R.sup.5 and R.sup.6 are independently alkyl, or aryl. In still
other embodiments R.sup.1, R.sup.2 and R.sup.3 are ethoxy or
methyl, L.sub.1 is (C.sub.10-C.sub.11) alkanyleno and R.sup.4,
R.sup.5 and R.sup.6 are independently methyl or phenyl.
[0076] In some embodiments, R.sup.4, R.sup.5 and R.sup.6 are
methyl. In other embodiments, R.sup.5 is phenyl.
[0077] In some embodiments, the compounds of Formula (II) have the
structure:
##STR00006##
[0078] Exemplary methods of synthesizing compounds described herein
are presented in Schemes 1-4, infra. Starting materials useful for
preparing compounds described herein are commercially available or
can be prepared by well-known synthetic methods. Other methods for
synthesis of the compounds described herein will be readily
apparent to the skilled artisan. Accordingly, the methods presented
in Schemes 1-4 herein are illustrative rather than
comprehensive.
[0079] Referring now to FIG. 1, 10-undecenoyl chloride 10 is
reacted with dimethylamine 11 to provide amide 12. Amide 12 is then
hydrosilylated with silane 13 in presence of a platinum catalyst to
yield compound 1.
[0080] Referring now to FIG. 2, the imine of undecylenic aldehyde
14 is formed upon treatment with methylamine 15. The imine 16 is
reduced with sodium borohydride 17 to provide amine 18 which is
hydrosilylated with silane 13 in the presence of a platinum
catalyst to provide the mono-methylated amine 19. Amine 19 may be
reacted with acetyl chloride 20, benzenesulfonyl chloride 21, ethyl
chloroformate 22, N,N-dimethylcarbamyl chloride 23 or
N,N-dimethylsulphamoyl chloride 24 to provide silicon compounds 3,
4, 5, 6 and 7, respectively.
[0081] Referring now to FIG. 3, 10-undecen-1-ol 25 is
hydrosilylated with silane 13 in the presence of a platinum
catalyst to provide silyl alcohol 26. Acylation of silyl alcohol 26
with acetyl chloride 20 or N,N-dimethylcarbamyl chloride 23,
provides silicon compounds 8 and 9, respectively.
[0082] Referring now to FIG. 4, bromide 37 is displaced with
dimethylamine 11 to provide the amine 38 which is then hydrosilated
with silane in the presence of platinum catalyst to yield the
silylamine 39. Compound 39 may be used as the ionizable component
of a mixed mode chromatography support.
[0083] Those of skill in the art will appreciate that the synthetic
strategies disclosed, supra, may be readily adapted to make silanes
with aryl, heteroaryl and heteroalkyl linkers by varying the
starting amine or acyl chloride or alkyl halide. Further, diverse
methods are known to those of skill in the art to accomplish the
transformations above (or equivalents thereof) and may be found in
any compendia of organic synthesis (see e.g., Harrison et al.,
"Compendium of Synthetic Organic Methods", Vols. 1-8 (John Wiley
and Sons, 1971-1996); "Beilstein Handbook of Organic Chemistry,"
Beilstein Institute of Organic Chemistry, Frankfurt, Germany;
Feiser et al., "Reagents for Organic Synthesis," Volumes 1-17,
Wiley Interscience; Trost et al., "Comprehensive Organic
Synthesis," Pergamon Press, 1991; "Theilheimer's Synthetic Methods
of Organic Chemistry," Volumes 1-45, Karger, 1991; March, "Advanced
Organic Chemistry," Wiley Interscience, 1991; Larock "Comprehensive
Organic Transformations," VCH Publishers, 1989; and Paquette,
"Encyclopedia of Reagents for Organic Synthesis," John Wiley &
Sons, 1995).
[0084] The compounds disclosed, supra, may be reacted with
substrates to form functionalized substrates, which can be used in
a wide range of different applications. The compounds disclosed,
supra, incorporate both hydrophobic and polar sites in one
molecular structure and have reproducible surface chemistries in
reactions with substrate surfaces.
[0085] In some embodiments, a compound of structural Formula (II)
is covalently bonded to a substrate. In other embodiments, the
compound of structural Formula (II) is covalently bonded to the
substrate by reaction of one or more of R.sup.1, R.sup.2 and
R.sup.3 groups with reactive groups on the substrate such, for
example, silanol, alkoxysilane, halosilane or aminosilane.
[0086] In some embodiments, a compound of structural Formula (II)
is covalently bonded through the SiR.sup.1(R.sup.2)(R.sup.3) group,
to another compound of structural Formula (II) by reaction with
reactive groups selected from the group consisting of silanol,
alkoxysilane or halosilane on the other compound. In this
embodiment, the two compounds are both covalently bonded to the
substrate.
[0087] In some embodiments, compositions of structural Formula
(III) are provided
##STR00007##
[0088] where R.sup.1, R.sup.3, L and Y are as defined, supra.
[0089] In other embodiments, compositions having the following
structures are provided:
##STR00008##
[0090] In still other embodiments, compositions of at least one
compound of structural Formula (II) and at least one compound of
structural Formula (IV) covalently bonded to a substrate are
provided where
##STR00009##
[0091] R.sup.8, R.sup.9, and R.sup.10 are independently alkyl,
alkoxy, alkoxycarbonyl, alkylsulfonyloxy, amino aryl,
aryloxycarbonyl, aryloxy, arylsulfonyloxy, halo or hydroxyl
optionally substituted with one or more of the same or different
R.sup.15 groups, provided that at least one of R.sup.1, R.sup.2 and
R.sup.3 are not alkyl, aryl or hydroxyl;
[0092] R.sup.15 is (C.sub.1-C.sub.6)alkyl;
[0093] L.sub.2 is alkyldiyl, heteroalkyldiyl, aryldiyl or
heteroaryldiyl; and
[0094] W is an ionizable group.
[0095] In other embodiments, a composition of structural Formula
(V) is provided
##STR00010##
[0096] where R.sup.1, R.sup.3, L.sub.1, L.sub.2, Y and W are as
defined, supra
[0097] In some embodiments, R.sup.8, R.sup.9 and R.sup.10 are
independently alkyl, alkoxy or halo. In other embodiments, R.sup.8,
R.sup.9 and R.sup.10 are alkoxy. In still other embodiments,
R.sup.8, R.sup.9 and R.sup.10 are alkyl or alkoxy. In still other
embodiments, R.sup.8, R.sup.9 and R.sup.10 are ethoxy or
methyl.
[0098] In some embodiments, L.sub.2 is alkyldiyl. In other
embodiments, L.sub.2 is alkanyldiyl. In still other embodiments,
L.sub.2 is alkyleno. In still other embodiments, L.sub.2 is
(C.sub.6-C.sub.20)alkanyleno. In still other embodiments, L.sub.2
is (C.sub.8-C.sub.15)alkanyleno. In still other embodiments,
L.sub.2 is (C.sub.10-C.sub.11) alkanyleno.
[0099] In some embodiments, W is --CO.sub.2, --SO.sub.3,
--P(O)(OR.sup.11)O--, --NR.sup.11R.sup.12, or
--N.sup.+R.sup.11R.sup.12R.sup.13, where R.sup.11, R.sup.12,
R.sup.13 are independently hydrogen or (C.sub.1-C.sub.6)alkyl. In
other embodiments, W is --NR.sup.11R.sup.12, or
--N.sup.+R.sup.11R.sup.12R.sup.13 wherein R.sup.11, R.sup.12 and
R.sup.13 are methyl.
[0100] In some embodiments, R.sup.1, R.sup.2, R.sup.3, R.sup.8,
R.sup.9 and R.sup.10 are independently alkyl, alkoxy or halo,
L.sub.1 and L.sub.2 are alkyldiyl, R.sup.4, R.sup.5 and R.sup.6 are
independently hydrogen, alkyl, or aryl and W is
--NR.sup.11R.sup.12, or --N.sup.+R.sup.11R.sup.12R.sup.13 where
R.sup.11, R.sup.12 and R.sup.13 are independently
(C.sub.1-C.sub.6)alkyl.
[0101] In some embodiments, R.sup.1, R.sup.2, R.sup.3, R.sup.8,
R.sup.9 and R.sup.10 are alkyl or alkoxy, L.sub.1 and L.sub.2 are
(C.sub.8-C.sub.15)alkanyleno, R.sup.4, R.sup.5 and R.sup.6 are
independently alkyl, or aryl and W is --NR.sup.11R.sup.12, or
--N.sup.+R.sup.11R.sup.12R.sup.13 where R.sup.11, R.sup.12 and
R.sup.13 are independently (C.sub.1-C.sub.6)alkyl. In other
embodiments, R.sup.1, R.sup.2, R.sup.3, R.sup.8, R.sup.9 and
R.sup.10 are ethoxy or methyl, L.sub.1 and L.sub.2 are
(C.sub.10-C.sub.11) alkanyleno, R.sup.4, R.sup.5 and R.sup.6 are
independently methyl or phenyl and W is --NR.sup.11R.sup.12, or
--NR.sup.+R.sup.11R.sup.12R.sup.13 where R.sup.11, R.sup.12 and
R.sup.13 are methyl. In a more specific embodiment, R.sup.4,
R.sup.5 and R.sup.6 are methyl. In another more specific
embodiment, R.sup.5 is phenyl.
[0102] In some embodiments, a compound of Formula (II) and the
compound of Formula (IV) are covalently bonded to the substrate by
reaction of one or more of R.sup.1, R.sup.2 and R.sup.3 and one or
more of R.sup.8, R.sup.9 and R.sup.10 with reactive groups on the
substrate selected from the group consisting of silanol,
alkoxysilane, halosilane or aminosilane. In other embodiments,
R.sup.2 and R.sup.9 are --OEt. In still other embodiments, a
composition where the compound of Formula (II) is
##STR00011##
and the compound of Formula (IV) is
##STR00012##
[0103] is provided. [0104] In still other embodiments a composition
of the following structure is provided:
##STR00013##
[0105] In some embodiments, compounds of Formulae (I) and (II) are
covalently attached to substrates as shown, supra. In these
embodiments, the polar group is disposed from the surface of the
substrate, which may improve hydrolytic stability of the
functionalized substrate. Compounds of Formulae (I) and (II) can be
attached to substrates (e.g., silica) to provide a functionalized
stationary phase for various chromatographic separations such as
reversed phase separations of surfactants. Further, compounds of
Formulae (I) and (II) may be mixed with silyl ligands containing
one or more ion exchange functionality (e.g., compounds of Formula
(IV) prior to reaction with the substrate to provide mixed mode
substrates of varying selectivity that also can be used for
reversed phase separations of surfactants.
[0106] Compounds of Formulae (I), (II) and (IV) may be covalently
bound to a substrate by reaction of R.sub.1, R.sub.2 or R.sub.3 of
the Si functionality with reactive groups on the substrate selected
from the group consisting of silanol, alkoxysilane, halosilane and
aminosilane moieties. In some embodiments, compounds of Formulae
(I), (II) and (IV) which are covalently bonded to a substrate may
be cross linked to one or more compounds of Formulae (I), (II) or
(IV) by reaction with reactive groups selected from the group
consisting of silanol, alkoxysilane or halosilane on other compound
of Formulae (I), (II) or (IV).
[0107] Compounds of Formulae (I), (II) and (IV) can be covalently
attached to a variety of substrates. Exemplary substrates include
materials that have a functional group that can react with
activated silyl groups in compounds of Formulae (I), (II) and (IV).
Thus, compounds of Formulae (I), (II) and (IV) can be attached, for
example, to silica based materials such as glass surfaces, or the
surfaces of other silicon oxide, titanium oxide, germanium oxide,
zirconium oxide and aluminum oxide based materials; and also to the
surfaces of various carbonized materials, metals, crosslinked and
non-crosslinked polymers, which contain suitable functional groups
for reacting with activated silyl groups. Examples of suitable
functional groups include silanols, alkoxysilanes, titanium
hydroxides, zirconium hydroxides, etc. Compounds of Formulae (I),
(II) and (IV) can also be incorporated into polymeric or sol-gel
networks by utilizing reactive silicon functionalities. Compounds
of Formulae (I), (II) and (IV) containing polymerizable groups or
groups that can be converted into radicals and/or ion-radicals
and/or ions, can be used for making polymeric materials and for
surface grafting, by utilizing those groups and/or reactive silicon
functionalities. The resulting materials can be applied for a
development of adsorbents, membranes, filters, microfluidic
devices, microchips, and functionalized surfaces for various types
of separation, detection, and analysis.
[0108] In some embodiments, mono- and multi-layered surfaces are
prepared by treating silica substrates with compounds of Formulae
(I), (II) and/or (IV). Compounds of Formulae (I), (II) and/or (IV)
can be covalently attached to a variety of substrates, such as
silica gel, zirconia, hybrid sol-gel/polymers or glass plates.
Suitable silica gels comprise non-porous, or porous silica
particles of different pore sizes, preferably from 20 .ANG. to 3000
.ANG. and more preferably, from 60 .ANG. to 2000 .ANG.; and of
different particle sizes, preferably, from 0.2 um to 1000 um, and
more preferably, from 2 um to 50 um. The attachment reaction can be
carried out in a slurry of silica gel in an inert solvent, such as
toluene, at elevated temperature. Water, acid or base catalyst can
be applied to enhance the surface coverage, depending on the type
of properties desired for the separation media.
[0109] Alternatively, an aminosilane compound, such as
bis(trimethoxysilylpropyl)amine can be used for modifying
underivatized silica gel by incorporating the reactive amino group
onto a surface. Then, a reagent, such as acyl chloride, carbamyl
chloride, sulfonyl chloride, or isocyanate, containing a proper
functional group, can be reacted with the aminated silica gel to
form the corresponding bonded phase.
[0110] The compositions described herein may be used as packing for
chromatography columns. The packing may be particles, monoliths
(i.e., material containing pores) or packed bed resins which are
loaded into a housing suitable for a chromatography column.
[0111] Also provided is a packing of a compound of structural
Formula (I) covalently bonded to a substrate and a compound of
structural Formula (IV) bonded to another substrate. In some
embodiments, the substrates are silica substrates.
[0112] The compositions described herein may be used to resolve a
variety of compounds. Generally, the compositions described herein
may be used to separate surfactants. The compositions described
herein may also be used, in some situations to resolve a mixture
including cationic surfactants, anionic surfactants and neutral
surfactants in a single chromatographic run.
[0113] This invention provides simple and versatile approaches to
produce a variety of novel solid supports with excellent hydrolytic
stability. The method of synthesis allows for efficient
incorporation of different functionalities onto the surfaces of the
substrates and silica substrates, in particular. The resulting
materials can be applied for development of adsorbents, membranes,
filters, microfluidic devices, microchips, and functionalized
surfaces for various types of separation, detection and
analysis.
6. EXAMPLES
[0114] The following examples are provided by way of illustration
only and not by way of limitation. Those of skill in the art will
readily recognize a variety of noncritical parameters that could be
changed or modified to yield essentially similar results.
6.1 Preparation of Compound 1
[0115] Dimethylamine was mixed with an excess of triethylamine (2.0
eq.) in anhydrous CH.sub.2Cl.sub.2 and kept at between about
0.degree. C. and about 5.degree. C. for 20 min. Then, a solution of
10-undecenoyl chloride (1.0 eq.) in CH.sub.2Cl.sub.2 was added
dropwise and the mixture was stirred at ambient temperature for 12
h. The reaction mixture was washed with water, dried over
Na.sub.2SO.sub.4 and the solvent was removed in vacuo to yield the
dimethylamide of 10-undecenoic acid. Excess dimethylethoxysilane
(10 eq.) was added to the amide followed by addition of a solution
of catalyst (0.1 mol %), (e.g., hexachloroplatinic acid in a
minimum amount of ethanol). After stirring at 50.degree. C. for 24
h, the silane and solvent were removed in vacuo to provide compound
1.
6.2 Example 2
Preparation of Compounds 3, 4, 5, 6 and 7
[0116] To a solution of 10-undecylenic aldehyde (1 eq.) in
anhydrous methanol was added excess methylamine in anhydrous
methanol (3 eq.). After 6 h at ambient temperature, the reaction
mixture was filtered followed by concentration in vacuo to give
imine 16.
[0117] Then imine 16 was reduced with sodium borohydride (6 eq.) in
methanol at ambient temperature for 24 h. After removal of all
volatiles in vacuo, amine 18 was obtained by partitioning the
residue between Et.sub.2O and H.sub.2O, drying over
Na.sub.2SO.sub.4 and concentrating in vacuo.
[0118] Then excess dimethylethoxysilane (10 eq.) was added to
compound 18 followed by addition of a solution of catalyst (0.1 mol
%), (e.g., hexachloroplatinic acid in a minimum amount of ethanol).
After stirring at 50.degree. C. for 24 h, the silane and solvent
were removed in vacuo to provide silyl compound 19.
[0119] Compound 19 was mixed with excess triethylamine (2.0 eq.) in
anhydrous CH.sub.2Cl.sub.2 and kept at between about 0.degree. C.
and about 5.degree. C. for 20 min. A solution of acetyl chloride
(1.2 equiv) in anhydrous CH.sub.2Cl.sub.2 was then added dropwise
and the mixture was stirred at ambient temperature for 12 h. All
volatiles were removed in vacuo and hexanes were added to
precipitate triethylammonium chloride salt. Compound 3 was obtained
after filtration and removal of solvent in vacuo.
[0120] Similarly, compounds 4, 5, 6 and 7 can be prepared by
reacting compound 19 with sulfonyl chloride, ethyl chloroformate,
N,N-dimethylcarbamyl chloride and N,N-dimethylsulphamoyl chloride,
respectively.
6.3 Example 3
Preparation of Compounds 8 and 9
[0121] Excess dimethylethoxysilane (10 equiv) was added to
10-undecen-1-ol (25) followed by addition of a solution of catalyst
(0.1 mol %), (e.g., hexachloroplatinic acid in a minimum amount of
ethanol). After stirring at 50.degree. C. for 24 h, the silane and
solvent were removed in vacuo to provide silyl compound 26.
[0122] Compound 26 was then mixed with excess triethylamine (2.0
eq.) in anhydrous CH.sub.2Cl.sub.2 and kept at between about
0.degree. C. and about 5.degree. C. for 20 min. Then, a solution of
acetyl chloride (1.2 eq.) in anhydrous CH.sub.2Cl.sub.2 was added
dropwise and the mixture stirred at ambient temperature for 12 h.
All volatiles were removed in vacuo and hexanes were added to
precipitate triethylammonium chloride salt. Compound 8 was obtained
after filtration and concentration in vacuo.
[0123] Similarly compound 9 can be prepared by reacting compound 26
with N,N-dimethylcarbamyl chloride.
6.4 Example 4
Preparation of Compound 39
[0124] A 5.degree. C. solution of 11-bromo-1-undecene in THF was
added dropwise to a solution of dimethylamine (10 eq.) in THF and
stirred at ambient temperature for 12 h. The volatiles were removed
in vacuo and the residue was partitioned between CH.sub.2Cl.sub.2
and H.sub.2O, dried over Na.sub.2SO.sub.4 followed by removal of
solvent in vacuo to provide 38.
[0125] Excess dimethylethoxysilane (10 eq.) was added to compound
38 followed by addition of a solution of catalyst (0.1 mol %),
(e.g., hexachloroplatinic acid in a minimum amount of ethanol).
After stirring at 50.degree. C. for 24 h, the silane and solvent
were removed in vacuo to provide silyl compound 39.
6.5 Example 5
Synthesis of Compositions 27, 28, 29, 30, 31, 32, 33, 34 and 35
[0126] Compounds 27, 28, 29, 30, 31, 32, 33, 34, or 35 in an inert
solvent (e.g., toluene at elevated temperature) were reacted with a
slurry of selected raw silica gel with the following physical
properties: average particle size, 5.0 .mu.m; specific surface
area, 300 m.sup.2/g; mean pore size, 120 .ANG.; pore volume, 1.00
mL/g. The addition of water, acid or base catalyst can be applied
to control the surface coverage. After a certain period of time
(from 3 h to 6 days), the reaction slurry was filtered, washed with
acetone, and dried in vacuum oven at 50.degree. C. for 5 h. A
proper end-capping reagent, such as a trialkylsilyl chloride, may
also be required to produce a packing material for chromatographic
separations.
6.6 Example 6
Synthesis of Composition 36
[0127] Compounds 27 and 39 were mixed in appropriate ratios in an
inert solvent such as toluene at elevated temperature. Then raw
silica with the characteristics described in Example 6 was added to
the above mixture to form a reaction slurry which was kept elevated
temperature for 3 days. The reaction slurry was filtered, washed
with acetone, and dried in vacuum oven at 50.degree. C. for 5 h to
give functionalized silica of composition 36. A proper end-capping
reagent, such as a trialkylsilyl chloride, may also be required to
produce a packing material for the reversed-phase chromatographic
separation.
6.7 Example 7
Polarity Test
[0128] HPLC chromatography of a test mixture containing uracil,
p-butyl benzoic acid and phenanthrene on composition 27 packed into
4.6.times.150 mm stainless steel tubes using traditional high
pressure slurry techniques yielded the results illustrated in FIG.
1. The mixture (injection volume of about 5 .mu.L) was eluted with
CH.sub.3CN/25 mM phosphate buffer at about pH 3.2 at a flow rate of
about 1 mL/min at about 30.degree. C. and was detected at 210 nm.
For comparison, a C8 column of the same column dimension and
prepared using the same silica substrate was also used in
chromatography of the test mixture.
[0129] FIG. 1 illustrates the high polarity of composition 27,
since the relative retention of the polar compound p-butyl benzoic
acid to neutral compound phenanthrene is higher on composition 27
than that on C8 column despite that fact that the latter has lower
carbon content. Enhancement of polarity may be due to the placement
of polar group at the end of the ligand furthest disposed from the
silica surface.
6.8 Example 8
Separation of Cationic, Nonionic and Anionic Surfactants
[0130] HPLC chromatography of a test mixture containing 7 common
surfactants including two cationic surfactants
(lauryldimethylbenzyl ammonium chloride and octylphenoxyethoxyethyl
dimethylbenzyl ammonium chloride), four anionic surfactants (sodium
salts of xylene sulfonate, dodecylbenzene sulfonate, decyl sulfate,
and dodecyl sulfate) and one nonionic surfactant (Triton X-100), on
composition 36 packed into 4.6.times.150 mm stainless steel tubes
using traditional high pressure slurry techniques yielded the
results illustrated in FIG. 6. The test mixture (injection volume
of about 25 .mu.L) was eluted with, CH.sub.3CN (A) and 0.1 M
NH.sub.4OAc at about pH 5.8 (B) mobile phases using a gradient
method (25% to 85% A in 30 min, then keep at 85% A for additional
10 min), at a flow rate of about 1 mL/min, at about 30.degree. C.
and was detected with evaporative light scattering detection
(ELS).
6.9 Example 9
Chromatographic Comparison: Analysis of Ethoxylated Surfactants
[0131] As shown in FIG. 7, a column packed with composition 36 was
compared with a conventional C18 column of the same column
dimension (5 .mu.m, in 4.6.times.150 mm stainless steel tubes) in
analysis of an ethoxylated nonionic surfactant Triton X-100. The
sample (injection volume of about 10 .mu.L) was eluted with
CH.sub.3CN and 0.1 M NH.sub.4OAc at about pH 5.4 (isocratic mobile
phases) at a flow rate of about 1 mL/min, at about 30.degree. C.
and was detected by UV at 225 nm.
6.10 Example 10
Chromatographic Comparison: Selectivity
[0132] HPLC chromatography of a test mixture containing 5 common
surfactants including four anionic surfactants (sodium salts of
xylene sulfonate, dodecylbenzene sulfonate, decyl sulfate and
dodecyl sulfate) and one nonionic surfactant (Triton X-100), on
composition 36 packed into 4.6.times.150 mm stainless steel tubes
using traditional high pressure slurry techniques yielded the
results illustrated in FIG. 8. The test mixture (injection volume
of about 25 .mu.L) was eluted with CH.sub.3CN (A) and 0.1 M
NH.sub.4OAc at about pH 5.8 (B) mobile phases using a gradient
method (25% to 85% A in 30 min, then keep at 85% A for additional
10 min) at a flow rate of about 1 mL/min at about 30.degree. C. and
detected with an evaporative light scatting detector. For
comparison, the same test mixture was also chromatographed on a C18
column of the same column dimension.
6.11 Example 11
Chromatographic Comparison: Analysis of Cationic Surfactants
[0133] As shown in FIG. 9, a column packed with composition 36 was
compared with a conventional C18 column of the same column
dimension (5 .mu.m, in 4.6.times.150 mm stainless steel tubes) in
analyzing the cationic surfactant lauryldimethylbenzyl ammonium
chloride. The sample (injection volume of about 5 .mu.L) was eluted
with CH.sub.3CN and 0.1 M NH.sub.4OAc at pH 5.4 (isocratic mobile
phases) at a flow rate of about 1 mL/min at about 30.degree. C. and
was detected by ELS. The column packed with composition 36 exhibits
superior peak shape over the C18 column.
6.12 Example 12
Chromatographic Comparison: Analysis of Sodium Xylene Sulfonate
[0134] As shown in FIG. 10, a column packed with composition 36 was
compared with a conventional C18 column of the same column
dimension (5 .mu.m, in 4.6.times.150 mm stainless steel tubes) in
analyzing the highly hydrophilic surfactant, sodium xylene
sulfonate. The sample (injection volume of about 5 .mu.L) was
eluted with, CH.sub.3CN/0.1 M NH.sub.4OAc, about pH 5.4 v/v 30/70
(isocratic mobile phases) at a flow rate of about 1 mL/min, at
about 30.degree. C. and detected by UV at about 225 nm. The column
packed with composition 36 exhibits excellent resolution among the
isomers with decent retention times.
[0135] Although the foregoing invention has been described in some
detail by way of illustration and example for purposes of clarity
of understanding, it will be readily apparent to one of ordinary
skill in the art in light of the teachings of this invention that
certain changes and modifications may be made thereto without
departing from the spirit or scope of the appended claims.
[0136] All publications and patent documents cited in this
specification are herein incorporated by reference in their
entirety.
* * * * *