U.S. patent application number 12/363895 was filed with the patent office on 2009-06-18 for adamantane derivatives and process for producing the same.
This patent application is currently assigned to Idemitsu Kosan Co., Ltd.. Invention is credited to Naoyoshi HATAKEYAMA, Yasunari Okada, Hidetoshi Ono, Shinji Tanaka.
Application Number | 20090156854 12/363895 |
Document ID | / |
Family ID | 34841840 |
Filed Date | 2009-06-18 |
United States Patent
Application |
20090156854 |
Kind Code |
A1 |
HATAKEYAMA; Naoyoshi ; et
al. |
June 18, 2009 |
ADAMANTANE DERIVATIVES AND PROCESS FOR PRODUCING THE SAME
Abstract
The present invention provides an adamantane derivative (I)
having a structure represented by the general formula (I); an
adamantane derivative (II) having a structure represented by the
general formula (II); and a process for producing those adamantane
derivatives. An alcohol form of an adamantane compound is reacted
with a sulfonyl compound to obtain the adamantane derivative (II),
which is then reacted with an alcohol to obtain the adamantane
derivative (I). The adamantane derivative (I) and adamantane
derivative (II) each having the structure represented by the
general formula (I) and general formula (II), respectively, is a
novel adamantyl (meth)acrylate compound and useful as a monomer for
functional resins such as a photosensitive resin in the field of
photolithography. ##STR00001##
Inventors: |
HATAKEYAMA; Naoyoshi;
(Ichihara-shi, JP) ; Tanaka; Shinji;
(Ichihara-shi, JP) ; Ono; Hidetoshi;
(Ichihara-shi, JP) ; Okada; Yasunari;
(Ichihara-shi, JP) |
Correspondence
Address: |
OBLON, SPIVAK, MCCLELLAND MAIER & NEUSTADT, P.C.
1940 DUKE STREET
ALEXANDRIA
VA
22314
US
|
Assignee: |
Idemitsu Kosan Co., Ltd.
Chiyoda-ku
JP
|
Family ID: |
34841840 |
Appl. No.: |
12/363895 |
Filed: |
February 2, 2009 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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10588080 |
Jan 10, 2007 |
7528279 |
|
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PCT/JP05/01404 |
Feb 1, 2005 |
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12363895 |
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Current U.S.
Class: |
558/429 ;
560/220 |
Current CPC
Class: |
C07C 303/28 20130101;
C07C 2603/74 20170501; C07C 69/54 20130101; C07C 309/66 20130101;
C07C 67/29 20130101; C07C 67/29 20130101; C07C 69/54 20130101; C07C
303/28 20130101; C07C 309/66 20130101 |
Class at
Publication: |
558/429 ;
560/220 |
International
Class: |
C07C 255/01 20060101
C07C255/01; C07C 69/533 20060101 C07C069/533 |
Foreign Application Data
Date |
Code |
Application Number |
Feb 5, 2004 |
JP |
2004-029034 |
Mar 10, 2004 |
JP |
2004-066626 |
Jul 27, 2004 |
JP |
2004-218686 |
Oct 8, 2004 |
JP |
2004-296542 |
Claims
1. An adamantane derivative, characterized by comprising a
structure represented by a general formula (I): ##STR00022## where
R represents a hydrogen atom, a methyl group, or a CF.sub.3 group,
Ys each represent an alkyl group having 1 to 10 carbon atoms, a
halogen atom, or a hydroxyl group, or two Ys are coupled to form
.dbd.O, and multiple Ys may be identical to or different from each
other, R1 represents an alkyl group or a cycloalkyl group having 1
to 10 carbon atoms, and may contain a hetero atom and/or a nitrile
group in part of its structure, k represents an integer of 0 to 14,
and m and n each independently represent an integer of 0 to 4.
2. The adamantane derivative according to claim 1, wherein a
substituent except Ys is present at a bridge head position.
3. The adamantane derivative according to claim 1, wherein R.sup.1
represents a group having tertiary carbon adjacent to O.
4-10. (canceled)
11. A process for producing an adamantane derivative represented by
the general formula (I): ##STR00023## where R represents a hydrogen
atom, a methyl group, or a CF.sub.3 group, Ys each represent an
alkyl group having 1 to 10 carbon atoms, a halogen atom, or a
hydroxyl group, or two Ys are coupled to form .dbd.O, and multiple
Ys may be identical to or different from each other, R.sup.1
represents an alkyl group or a cycloalkyl group having 1 to 10
carbon atoms, and may contain a hetero atom and/or a nitrile group
in part of its structure, k represents an integer of 0 to 14, and m
and n each independently represent an integer of 0 to 4, the
process being characterized by comprising reacting an adamantane
derivative represented by the general formula (II): ##STR00024##
where R.sup.2 represents an alkyl group having 1 to 10 carbon
atoms, a phenyl group, an alkylphenyl group, or a CF.sub.3 group,
R, Ys, k, m, and n each have the same meaning as that described
above, with an alcohol.
12. The process for producing an adamantane derivative according to
claim 11, wherein 3-methanesulfonyloxy-1-adamantyl (meth)acrylate
is reacted with the alcohol.
13. The process for producing an adamantane derivative according to
claim 11, wherein the alcohol comprises a tertiary alcohol.
Description
TECHNICAL FIELD
[0001] The present invention relates to a novel adamantane
derivative and a process for producing the same. More specifically,
the present invention relates to novel alkoxy group-substituted
adamantyl (meth)acrylates and alkylsulfonyloxy-substituted
adamantyl (meth)acrylates useful as monomers for functional resins
such as a photosensitive resin in the field of photolithography,
and a process for producing each of those adamantane derivatives
efficiently.
BACKGROUND ART
[0002] Adamantane has a structure in which four cyclohexane rings
are condensed in a cage fashion, and is a compound which has high
symmetry and is stable. A derivative of adamantane is known to be
useful as, for example, a raw material for a drug or a raw material
for a high functionally industrial material because the derivative
shows a specific function. Attempts have been made to use the
derivative in an optical disk substrate, an optical fiber, a lens,
or the like because the derivative has, for example, optical
properties and heat resistance (Patent Document 1 and Patent
Document 2).
[0003] In addition, attempts have been made to use adamantane
esters as raw materials for resins for photoresist by utilizing the
acid sensitivity, resistance to dry etching, permeability to
ultraviolet light, and the like of the adamantane esters (Patent
Document 3).
[0004] Meanwhile, the miniaturization of a semiconductor device has
progressed in recent years. In association with the progress,
additional miniaturization has been demanded in a lithography step
in the production of the semiconductor device. Therefore,
investigation has been conducted into various methods of forming a
fine pattern by using a photoresist material corresponding to light
to be applied having a short wavelength such as KrF, ArF, or
F.sub.2 excimer laser light. In addition, the appearance of a new
photoresist material capable of corresponding to light to be
applied having a short wavelength such as the above-mentioned
excimer laser light is desired. A monomer in to which a hydroxyl
group is introduced for improving the adhesiveness of a silicon
substrate has been conventionally known (Patent Document 4). A
photoresist material having a functionally functional group that
has not been known heretofore is desired.
[0005] Patent Document 1: Japanese Patent Application Laid-Open No.
Heisei 6 (1994)-305044
[0006] Patent Document 2: Japanese Patent Application Laid-Open No.
Heisei (1997)-302077
[0007] Patent Document 3: Japanese Patent Application Laid-Open No.
Heisei 4 (1992)-39665
[0008] Patent Document 4: Japanese Patent Application Laid-Open No.
Showa 63 (1988)-33350
DISCLOSURE OF THE INVENTION
[0009] The present invention has been made under such
circumstances, and an object of the present invention is to provide
a novel adamantane derivative useful as a monomer for a functional
resin such as a photosensitive resin in the field of
photolithography, and a process for producing the same.
[0010] The inventors of the present invention have made extensive
studies with a view to achieving the above object. As a result,
they have found that alkoxy-substituted adamantyl (meth)acrylates
and methanesulfonyloxy-substituted adamantyl (meth)acrylates each
having a specific structure are novel compounds and are suitable
for the object, and that each of these compounds can be efficiently
produced by reacting an alcohol form having a corresponding
adamantyl group as a raw material.
[0011] The present invention has been completed on the basis of
such findings.
[0012] That is, the present invention provides the following
adamantane derivatives and a process for producing the same.
[0013] [1] An adamantane derivative, characterized by comprising a
structure represented by a general formula (I):
##STR00002##
where R represents a hydrogen atom, a methyl group, or a CF.sub.3
group, Ys each represent an alkyl group having 1 to 10 carbon
atoms, a halogen atom, or a hydroxyl group, or two Ys are coupled
to form .dbd.O, and multiple Ys may be identical to or different
from each other, R.sup.1 represents an alkyl group or a cycloalkyl
group having 1 to 10 carbon atoms, and may contain a hetero atom
and/or a nitrile group in part of its structure, k represents an
integer of 0 to 14, and m and n each independently represent an
integer of 0 to 4.
[0014] [2] An adamantane derivative according to the above item
[1], in which a substituent except Ys is present at a bridge head
position.
[0015] [3] An adamantane derivative according to the above item [1]
or [2], in which R.sup.1 represents a group having tertiary carbon
adjacent to O.
[0016] [4] An adamantane derivative, characterized by comprising a
structure represented by a general formula (II):
##STR00003##
where R represents a hydrogen atom, a methyl group, or a CF.sub.3
group, R.sup.2 represents an alkyl group having 1 to 10 carbon
atoms, a phenyl group, an alkylphenyl group, or a CF.sub.3 group,
Ys each represent an alkyl group having 1 to 10 carbon atoms, a
halogen atom, or a hydroxyl group, or two Ys are coupled to form
.dbd.O, and multiple Ys may be identical to or different from each
other, k represents an integer of 0 to 14, and m and n each
independently represent an integer of 0 to 4.
[0017] [5] An adamantane derivative according to the above item
[4], in which R.sup.2 represents a methyl group.
[0018] [6] A process for producing an adamantane derivative having
a structure represented by the general formula (II):
##STR00004##
where R represents a hydrogen atom, a methyl group, or a CF.sub.3
group, R.sup.2 represents an alkyl group having 1 to 10 carbon
atoms, a phenyl group, an alkylphenyl group, or a CF.sub.3 group,
Ys each represent an alkyl group having 1 to 10 carbon atoms, a
halogen atom, or a hydroxyl group, or two Ys are coupled to form
.dbd.O, and multiple Ys may be identical to or different from each
other, k represents an integer of 0 to 14, and m and n each
independently represent an integer of 0 to 4, the process being
characterized by comprising reacting an alcohol form of an
adamantane compound represented by a general formula (III):
##STR00005##
where R, Ys, k, m, and n each have the same meaning as that
described above, with a sulfonyl compound represented by a general
formula (IV):
##STR00006##
where R.sup.2 represents an alkyl group having 1 to 10 carbon
atoms, a phenyl group, an alkylphenyl group, or a CF.sub.3 group,
and X represents a hydroxyl group or a halogen atom.
[0019] [7] A process for producing an adamantane derivative
according to the above item [6], in which the alcohol form of the
adamantane compound represented by the general formula (III) and
the sulfonyl compound represented by the general formula (IV) are
reacted with each other in an organic solvent having a dielectric
constant at 20.degree. C. of 8 or less.
[0020] [8] A process for producing an adamantane derivative
according to the above item [6] or [7], in which the sulfonyl
compound represented by the general formula (IV) comprises
methanesulfonyl halide.
[0021] [9] A process for producing an adamantane derivative
according to any one of the above item [6] to [8], in which, after
the alcohol form of the adamantane compound represented by the
general formula (III) and the sulfonyl compound represented by the
general formula (IV) have been reacted with each other, a reaction
product is separated from a liquid after completion of the
reaction, a poor solvent for a by-product polymer in the reaction
product is added to the reaction product, and a precipitate of the
by-product polymer to be produced is removed.
[0022] [10] A process for producing an adamantane derivative
according to the above item [9], in which the poor solvent for the
by-product polymer comprises methanol.
[0023] [11] A process for producing an adamantane derivative
represented by the general formula (I):
##STR00007##
where R represents a hydrogen atom, a methyl group, or a CF.sub.3
group, Ys each represent an alkyl group having 1 to 10 carbon
atoms, a halogen atom, or a hydroxyl group, or two Ys are coupled
to form .dbd.O, and multiple Ys may be identical to or different
from each other, R.sup.1 represents an alkyl group or a cycloalkyl
group having 1 to 10 carbon atoms, and may contain a hetero atom
and/or a nitrile group in part of its structure, k represents an
integer of 0 to 14, and m and n each independently represent an
integer of 0 to 4, the process being characterized by comprising
reacting an adamantane derivative represented by the general
formula (II):
##STR00008##
where R.sup.2 represents an alkyl group having 1 to 10 carbon
atoms, a phenyl group, an alkylphenyl group, or a CF.sub.3 group,
R, Ys, k, m, and n each have the same meaning as that described
above, with an alcohol.
[0024] [12] A process producing an adamantane derivative according
to the above item (11), in which
3-methanesulfonyloxy-1-adamantyl(meth)acrylate is reacted with the
alcohol.
[0025] [13] A process for producing an adamantane derivative
according to the above item (11) or (12), in which the alcohol
comprises a tertiary alcohol.
BEST MODE FOR CARRYING OUT THE INVENTION
[0026] Hereinafter, a compound represented by a general formula (I)
of the present invention is represented as an adamantane derivative
(I), and a compound represented by a general formula (II) of the
present invention is represented as an adamantane derivative (II).
Each of those adamantane derivatives is a novel compound.
[0027] Next, those adamantane derivatives and a process for
producing each of them will be described.
[0028] First, the adamantane derivative (I) of the present
invention is one of the alkoxy group-substituted adamantyl
(meth)acrylates each having a structure represented by the general
formula (I).
##STR00009##
[0029] In the general formula (I), R represents a hydrogen atom, a
methyl group, or a trifluoromethyl group, Ys each represent an
alkyl group having 1 to 10 carbon atoms, a halogen atom, or a
hydroxyl group, or two Ys are coupled to form .dbd.O. Multiple Ys
may be identical to or different from each other. R.sup.1
represents an alkyl group having 1 to 10 carbon atoms, and may
contain a hetero atom and/or a nitrile group in part of its
structure. k represents an integer of 0 to 14, and m and n each
independently represent an integer of 0 or more, or preferably 0 or
1. When m represents 0 and n represents 0, a structure in which
oxygen is directly bound to an adamantyl group is shown.
[0030] Examples of an alkyl group having 1 to 10 carbon atoms in
each of Ys and R.sup.1 in the foregoing include a methyl group, an
ethyl group, various propyl groups, various butyl groups, various
pentyl groups, various hexyl groups, various heptyl groups, various
octyl groups, various nonyl groups, and various decyl groups. Each
of those groups may be linear or branched. The alkyl group may be
substituted by a halogen atom, a hydroxyl group, or the like. In
addition, R.sup.1 represents a cycloalkyl group as well. When the
alkyl group or cycloalkyl group represented by R.sup.1 contains a
hetero atom and/or a nitrile group in part of its structure,
irregularities appearing on the side surface of a resist pattern
are additionally alleviated when the derivative is used as a
photosensitive resin.
[0031] Specific examples of R.sup.1 may include the followings.
Examples of R.sup.1 bound with a primary carbon include a methyl
group, ethyl group, 1-propyl group, 1-butyl group, 1-pentyl group,
3-methyl-1-butyl group, 2-methyl-1-butyl group,
2,2-dimethyl-1-butyl group, 3,3-dimethyl-1-butyl group,
cyclohexylmethyl group, 1-adamantylmethyl group,
3-hydroxymethyl-1-adamantylmethyl group, 2-hydroxy-1-ethyl group,
2,3-bishydroxypropyl group, 2,2,2-tris(hydroxymethyl)-ethyl group,
and 2-chloro-1-ethyl group.
[0032] Examples of R.sup.1 bound with a secondary carbon include a
2-propyl group, 2-butyl group, 2-pentyl group, 3-methyl-2-butyl
group, 3,3-dimethyl-2-butyl group, cyclohexyl group, 2-adamantyl
group, 4-oxo-2-adamantyl group, 1-methoxy-2-propyl group, and
1,3-dihydroxy-2-propyl group.
[0033] Examples of R.sup.1 bound with a tertiary carbon include a
2-methyl-2-propyl group (tert-butyl group), 2-methyl-2-butyl group
(tert-pentyl group), 2,3-dimethyl-2-butyl group (tert-hexyl group),
1-adamantyl group, 3-hydroxy-1-adamantyl group, 4-oxo-1-adamantyl
group, perfluoro-1-adamantyl group, perfluoro-3-hydroxy-1-adamantyl
group, 1-methylcyclohexyl group, 1-ethylcyclopentyl group, and
2-methyl-2-adamantyl group.
[0034] R.sup.1 preferably represents a group having tertiary carbon
adjacent to O from the viewpoint of usefulness of the derivative as
a novel substance. Of those, R.sup.1 preferably represents a
tert-butyl group, a tert-pentyl group, or a tert-hexyl group. In
addition, a substituent except Ys is preferably present at a bridge
head position.
[0035] Examples of a halogen atom in each of Ys include fluorine,
chlorine, bromine, and iodine.
[0036] Examples of particularly preferable compounds represented by
the above-mentioned general formula (I) include
3-tert-pentyloxy-1-adamantyl methacrylate,
3-tert-butyloxy-1-adamantyl acrylate, 3-tert-pentyloxy-1-adamantyl
2-trifluoromethyl acrylate, 3-tert-hexyloxy-1-adamantyl
methacrylate, 3-tert-pentyloxymethyl-1-adamantylmethyl
methacrylate, 3-tert-butyloxymethyl-1-adamantylmethyl acylate,
3-tert-pentyloxymethyl-1-adamantylmethyl 2-trifluoromethyl
acrylate, 3-tert-butyloxy-perfluoro-1-adamantylmethacrylate, and
3-tert-pentyloxy-perfluoro-1-adamantyl acrylate.
[0037] Next, the adamantane derivative (II) will be described. The
adamantane derivative (II) of the present invention is one of the
sulfonyloxy-substituted adamantyl (meth)acrylates each having a
structure represented by the general formula (II).
##STR00010##
[0038] In the general formula (II), R represents a hydrogen atom, a
methyl group, or a CF.sub.3 group, R.sup.2 represents an alkyl
group having 1 to 10 carbon atoms, a phenyl group, an alkylphenyl
group, or a CF.sub.3 group, Ys each represent an alkyl group having
1 to 10 carbon atoms, a halogen atom, or a hydroxyl group, or two
Ys are coupled to form .dbd.O. Multiple Ys may be identical to or
different from each other. k represents an integer of 0 to 14, and
m and n each independently represent an integer of 0 to 4. When m
represents 0 and n represents 0, a structure in which oxygen is
directly bound to an adamantyl group is shown.
[0039] Examples of an alkyl group having 1 to 10 carbon atoms in
R.sup.2 in the foregoing include those described above. Examples of
an alkylphenyl group include a methylphenyl group, an ethylphenyl
group, and a propylphenyl group.
[0040] Examples of adamantane derivatives (II) represented by the
above-mentioned general formula (II) preferably include, as those
in each of which R.sup.2 represents a methyl group,
3-methanesulfonyloxy-1-adamantyl methacrylate,
3-methanesulfonyloxy-1-adamantyl acylate,
3-methanesulfonyloxy-1-adamantyl 2-trifluoromethyl acrylate,
1-methanesulfonyloxy-4-adamantyl methacrylate,
1-methanesulfonyloxy-4-adamantyl acrylate,
1-methanesulfonyloxy-4-adamantyl 2-trifluoromethyl acrylate,
3-methanesulfonyloxymethyl-1-adamantylmethyl methacrylate,
3-methanesulfonyloxymethyl-1-adamantylmethyl acrylate,
3-methanesulfonyloxymethyl-1-adamantylmethyl 2-trifluoromethyl
acrylate, 3-methanesulfonyloxy-perfluoro-1-adamantyl methacrylate,
and 3-methanesulfonyloxy-perfluoro-1-adamantyl acrylate.
[0041] Next, a preferable process for producing each of the
adamantane derivative (I) and the adamantane derivative (II) will
be described.
[0042] First, the adamantane derivative (II) is produced by
reacting an alcohol form of an adamantane compound represented by
the general formula (III) with a sulfonyl compound represented by
the general formula (IV).
[0043] Examples of an alcohol of the adamantane compound
represented by the general formula (III) as a raw material include
hydroxy group-containing adamantyl (meth)acrylates such as a
3-hydroxy-1-adamantyl methacrylate, 3-hydroxy-1-adamantyl acylate,
3-hydroxy-1-adamantyl 2-trifluoromethyl acrylate,
3-hydroxymethyl-1-adamantylmethyl methacrylate,
3-hydroxymethyl-1-adamantylmethyl acrylate,
3-hydroxymethyl-1-adamantylmethyl 2-trifluoromethyl acrylate,
3-hydroxy-perfluoro-1-adamantyl methacrylate, and
3-hydroxy-perfluoro-1-adamantyl acrylate.
[0044] Next, in the sulfonyl compound represented by the general
formula (IV), X preferably represents a halogen atom rather than a
hydroxyl group from the viewpoint of reactivity, and particularly
preferably represents a chlorine atom from an industrial viewpoint.
Examples of the sulfonyl compound include methanesulfonyl chloride,
ethanesulfonyl chloride, propanensulfonyl chloride,
p-toluenesulfonyl chloride, and trifluoromethanesulfonyl chloride.
Of those, methanesulfonyl chloride is preferable.
[0045] A charge ratio between the alcohol form of the adamantane
compound represented by the general formula (III) and the sulfonyl
compound represented by the general formula (IV) is preferably such
that the sulfonyl compound is charged in an amount in the range of
1 to 1.5 mol with respect to 1 mol of the adamantane compound.
[0046] In this reaction, a base is generally used as a catalyst,
and a solvent is used as required.
[0047] Examples of the base include: sodium amide; triethylamine;
tributylamine; trioctylamine; pyridine; N,N-dimethylaniline;
1,5-diazabicyclo[4.3.0]nonene-5 (DBN);
1,8-diazabicyclo[5.4.0]undecene-7 (DBU); sodium hydroxide;
potassium hydroxide; sodium hydride; potassium carbonate; silver
oxide; sodium methoxide; and potassium t-butoxide. One kind of
those catalysts may be used alone, or two or more kinds of them may
be used in combination.
[0048] In this reaction, a solvent is ordinarily used. A solvent
having a solubility for each of hydroxyl group-containing adamantyl
(meth)acrylates as raw materials of 0.5 mass % or more, or
desirably 5 mass % or more at a reaction temperature is preferably
used as the solvent. The amount of the solvent is such that the
concentration of the hydroxyl group-containing adamantyl
(meth)acrylates in a reaction mixture is 0.5 mass % or more, or
desirably 5 mass % or more. At this time, the adamantane derivative
(II), which may be in a suspended state, is desirably dissolved. In
addition, moisture in the solvent is desirably removed before use.
Specific examples of the solvent include: hydrocarbon-based
solvents such as n-hexane and n-heptane; ether-based solvents such
as diethyl ether and tetrahydrofuran; halogen-based solvents such
as dichloromethane and carbon tetrachloride; dimethylsulfoxide; and
N,N-dimethylsulfoxide. One kind of those solvents may be used
alone, or two or more kinds of them may be used as a mixture.
[0049] Of those, an organic solvent having a dielectric constant at
20.degree. C. of 8 or less is preferably used as the solvent. The
use of such solvent having a low dielectric constant can not only
produce the target adamantane derivative (II) in high yield but
also suppress the production of a polymer, thereby resulting in an
improvement in handleability. Specific examples of such solvent
include: hydrocarbon-based solvents such as toluene, n-hexane,
n-heptane, and cyclohexane; ester-based solvents such as ethyl
acetate; and mixed solvents of these solvents and ether-based
solvents such as diethyl ether and tetrahydrofuran. One kind of
those solvents may be used alone, or two or more kinds of them may
be used as a mixture.
[0050] When the above-described solvent having a low dielectric
constant is used as the solvent, salt is removed through water
washing after a reaction, and then the adamantane derivative (II)
can be separated through crystallization.
[0051] A reaction temperature to be ordinarily adopted is in the
range of -200 to 200.degree. C. As long as the reaction temperature
is in the range, a reaction rate does not reduce, and a reaction
time is not excessively long. In addition, the amount of a polymer
to be produced as a by-product does not increase. The reaction
temperature is in the range of preferably -200 to 100.degree. C.,
or more preferably -50 to 50.degree. C.
[0052] A reaction pressure in terms of an absolute pressure to be
ordinarily adopted is in the range of 0.01 to 10 MPa. A reaction
pressure in the range is economical because the reaction pressure
in the range eliminates the need for a special pressure-resistant
device. The reaction pressure is preferably in the range of normal
pressure to 1 MPa.
[0053] A reaction time is in the range of ordinarily 1 minute to 24
hours, preferably 5 minutes to 6 hours, or more preferably 30
minutes to 6 hours.
[0054] When R.sup.2 in the sulfonyl compound represented by the
general formula (II) indicates a methyl group, the adamantane
derivative can be separated from a by-product by: separating a
reaction product from a liquid after the completion of a reaction;
adding, to the reaction product, a poor solvent for a by-product
polymer in the reaction product; and removing the precipitate of
the by-product polymer to be produced. In that case, methanol,
ethanol, diethyl ether, or the like can be used as the poor
solvent, and, of those, methanol is preferable.
[0055] To be specific, water is added to the reaction after the
completion of a reaction to deactivate methanesulfonyl halide.
After that, the solvent is distilled off, the residue is washed,
and a catalyst is removed. Next, a poor solvent for a by-product
polymer in the residue, for example, methanol is added to
precipitate the by-product polymer. After the precipitate has been
removed by means of a method such as filtration, the poor solvent
is distilled off. Next, the residue after the poor solvent has been
distilled off is recrystallized by using, for example, an
ether-based solvent. As a result, the target adamantane derivative
(II) in which R.sup.2 represents a methyl group can be obtained at
a high purity.
[0056] Distillation, crystallization, column separation, or the
like can be adopted for purifying a target reaction product. It is
recommended that a purification method be selected depending on the
properties of a product and the kind of an impurity.
[0057] The adamantane derivative (I) can be obtained by: reacting
the alcohol form of the adamantane compound represented by the
general formula (III) with a sulfonyl halide compound represented
by the general formula (IV) to provide the adamantane derivative
(II); and reacting the adamantane derivative (II) with an alcohol.
Alternatively, the sulfonyl halide compound may be etherified in
advance, and the resultant may be finally turned into a
(meth)acrylate.
[0058] That is, a process for producing the adamantane derivative
(I) includes: a step of reacting the alcohol form of the adamantane
compound represented by the general formula (III) with a
sulfonyloxy halide compound represented by the following general
formula (IV):
##STR00011##
where R.sup.2 has the same meaning as that described above and X
represents a halogen atom to provide a sulfonyloxy form represented
by the following general formula (II):
##STR00012##
where R, R.sup.2, Ys, k, m, and n each have the same meaning as
that described above (a first step: a sulfonylating step); and
[0059] a step of reacting the sulfonyloxy form with an alcohol
represented by the following general formula (V):
R.sup.1--OH (V)
where R.sup.1 has the same meaning as that described above to
provide the target adamantane derivative (I) (a second step: an
etherifying step). Hereinafter, those steps will be sequentially
described.
[0060] (1) First Step (Sulfonylating Step)
[0061] The sulfonyloxy halide compound to be used in the first step
is similar to the above-described sulfonyl compound represented by
the general formula (IV), and the sulfonyloxy form is similar to
the above-described adamantane derivative (II) represented by the
general formula (II). Therefore, the sulfonyloxy form (II) can be
produced by means of a process similar to the above process for
producing the adamantane derivative (II).
[0062] (2) Second Step (Etherifying Step)
[0063] The second step is a step of reacting the sulfonyloxy form
(II) with the alcohol represented by the general formula (V) to
provide the target adamantane derivative (I). Any one of
methanesulfonyloxy-substituted adamantyl (meth)acrylates such as
3-methanesulfonyloxy-1-adamantyl (meth)acrylate is suitably used as
the sulfonyloxy form (II).
[0064] Any one of those described above can be used as R.sup.1 in
the alcohol represented by the general formula (V); provided that a
tertiary alcohol having tertiary carbon adjacent to O such as
tert-butyl alcohol, tert-pentyl alcohol, or tert-hexyl alcohol is
preferable from the viewpoint of usefulness of the present
invention as a novel substance. A charge ratio has only to be such
that the alcohol is charged in an amount in the range of 1 to 1.5
mol with respect to 1 mol of the sulfonyloxy form (II) obtained in
the first step.
[0065] In this reaction, a base is generally used as a catalyst,
and a solvent is used as required.
[0066] Examples of the base include: sodium amide; triethylamine;
tributylamine; trioctylamine; pyridine; N,N-dimethylaniline;
1,5-diazabicyclo[4.3.0]nonene-5 (DBN);
1,8-diazabicyclo[5.4.0]undecene-7 (DBU); sodium hydroxide;
potassium hydroxide; sodium hydride; potassium carbonate; silver
oxide; sodium methoxide; and potassium t-butoxide. One kind of
those catalysts may be used alone, or two or more kinds of them may
be used in combination.
[0067] A solvent to be used in the etherifying step preferably has
a solubility for the sulfonyloxy form (II) of 0.5 mass % or more,
or desirably 5 mass % or more at a reaction temperature. It is
recommended that the amount of the solvent be such that the
concentration of the sulfonyloxy form (II) in a reaction mixture is
0.5 mass % or more, or desirably 5 mass % or more. At this time,
the sulfonyloxy form (II), which may be in a suspended state, is
desirably dissolved. In addition, moisture in the solvent is
desirably removed before use. Specific examples of the solvent
include: hydrocarbon-based solvents such as n-hexane and n-heptane;
ether-based solvents such as diethyl ether and tetrahydrofuran;
halogen-based solvents such as dichloromethane and carbon
tetrachloride; dimethylsulfoxide; and N,N-dimethylsulfoxide. One
kind of those solvents may be used alone, or two or more kinds of
them may be used as a mixture.
[0068] A reaction temperature to be ordinarily adopted is in the
range of -200 to 200.degree. C. As long as the reaction temperature
is in the range, a reaction rate does not reduce, and a reaction
time is not excessively long. In addition, the amount of a polymer
to be produced as a by-product does not increase. The reaction
temperature is preferably in the range of 100 to 150.degree. C.
[0069] A reaction pressure in terms of an absolute pressure to be
ordinarily adopted is in the range of 0.01 to 10 MPa. A reaction
pressure in the range is economical because the reaction pressure
in the range eliminates the need for a special pressure-resistant
device. The reaction pressure is preferably in the range of normal
pressure to 10 MPa.
[0070] A reaction time is ordinarily in the range of 1 to 48
hours.
[0071] A target compound can be purified and separated by:
hydrolyzing the sulfonyloxy form (II) that is unreacted with an
alkaline aqueous solution such as an aqueous solution of sodium
hydrogen carbonate to turn the sulfonyloxy form into an alcohol
form corresponding to the general formula (III); and adsorbing the
alcohol form to silica gel or the like.
[0072] The resultant compound can be identified by using, for
example, gas chromatography (GC), liquid chromatography (LC), gas
chromatography-mass spectrometry (GC-MS), nuclear magnetic
resonance spectroscopy (NMR), infrared spectroscopy (IR), or a
melting-point apparatus.
EXAMPLES
[0073] Next, the present invention will be described in more detail
by way of examples. However, the present invention is not limited
by these examples at all.
[0074] A value for the dielectric constant of a solvent is a
numerical value according to "Solvent Pocketbook new edition"
(Ohmsha, Ltd.), edited by the Society of Synthetic Organic
Chemistry, Japan and "Solvent Handbook" (Koudansha Scientific) by
Shozo Asahara et al., and a value for the dielectric constant of a
mixed solvent (Example 10) is a numerical value calculated on the
basis of an additive rule.
Example 1
Production of Adamantane Derivative (I)
[0075] Synthesis of 3-tert-pentyloxy-1-adamantyl methacrylate
represented by the following structural formula:
##STR00013##
[0076] (1) Sulfonylating Step
[0077] A 2-L glass reactor was equipped with a stirring device.
118.16 g (500 mmol) of 3-hydroxy-1-adamantyl methacrylate
(ADAMANTATE HM, manufactured by Idemitsu Kosan Co., Ltd.), 104.5 ml
(750 mmol) of dry triethylamine, and 1 l of dry tetrahydrofuran
were added to the reactor, and the mixture was stirred while the
temperature of the mixture was cooled to 0.degree. C. in an ice
bath. 46.4 ml (600 mmol) of methanesulfonyl chloride were added to
the mixture, and the whole was stirred for 5 minutes, followed by
gas chromatography analysis. As a result, it was confirmed that
3-methanesulfonyloxy-1-adamantyl methacrylate was obtained at a
degree of conversion of 92.6% and a selectivity of 99.8%. 50 ml of
water were added to the resultant to deactivate unreacted
methanesulfonyl chloride, and tetrahydrofuran was removed by using
an evaporator. The resultant was transferred to a 2-L separating
funnel, 600 ml of diethyl ether and 550 ml of water were added to
the resultant twice, the mixture was washed with water twice, and a
triethylamine salt and 1.01 g of a polymer were removed. 12.0 g
(100 mmol) of anhydrous magnesium sulfate were added to the
resultant, and the whole was dehydrated. After that, magnesium
sulfate was removed by means of filtration. The resultant was
evaporated in such a manner that diethyl ether would be removed,
followed by gas chromatography (GC) analysis and GPC analysis. As a
result, it was confirmed that 3-methanesulfonyloxy-1-adamantyl
methacrylate was obtained in a yield of 156.26 g and at a purity of
91.3% (GC) or 97.8% (GPC).
[0078] (2) Etherifying Step
[0079] A 2-L glass reactor was equipped with a stirring device. The
product obtained in the above item (1) was loaded into the reactor.
750.0 ml (6.849 mmol) of dry 2-methyl-2-butanol, 80.0 ml (535 mmol)
of dry 1,8-diazabicyclo[5.4.0]-7-undecene (DBU), and 0.30 g (2,000
mass ppm) of methoquinone were added to the reactor, and the
mixture was stirred. The temperature of an oil bath was set to
120.degree. C., and reflux was performed for 36 hours. In addition,
0.03 g (200 mass ppm) of methoquinone was sequentially added every
6 hours. Gas chromatography analysis confirmed that a target
product was obtained at a degree of conversion of 86.9% and a
selectivity of 99.8%. To turn 3-methanesulfonyloxy-1-adamantyl
methacrylate that had not been converted into 3-hydroxy-1-adamantyl
methacrylate, 100 ml of a saturated aqueous solution of sodium
hydrogen carbonate were added, and the mixture was stirred. The
mixture was stirred at 60.degree. C. for an additional 8 hours.
2-methyl-2-butanol was removed by using an evaporator. The
resultant was transferred to a 2-L separating funnel, 600 ml of
diethyl ether and 550 ml of water were added to the resultant
twice, the mixture was washed with water twice, and a DBU salt was
removed. 12.0 g (100 mmol) of anhydrous magnesium sulfate were
added to the resultant, and the whole was dehydrated. After that,
magnesium sulfate was removed by means of filtration. The resultant
was evaporated in such a manner that diethyl ether would be
removed, followed by gas chromatography analysis. As a result, it
was confirmed that a target product was obtained in a yield of
149.1 g and at a purity of 80.7%. The target product was dissolved
into 1 L of hexane, and the solution was filtered and decolorized
by using 100 g of silica gel to which 3-hydroxy-1-adamantyl
methacrylate had been adsorbed. n-hexane was removed by using an
evaporator, whereby 81.0 g of a colorless, transparent liquid were
obtained. Gas chromatography analysis confirmed that a target
product was obtained at a purity of 99.8%. Data on each of
.sup.1H-NMR, .sup.13C-NMR, and GC-MS is shown below.
[0080] Nuclear magnetic resonance analysis (NMR): CDCl.sub.3
[0081] .sup.1H-NMR (500 MHz): 0.85 (t, J=7.7 Hz, 3H, o); 1.21 (s,
6H, m), 1.43 (q, J=7.4 Hz, 2H, n); 1.48 (m, 2H, h or i); 1.80
(br-s, 4H, f or j); 1.85 (s, 3H, a); 1.97 (d, J=11.5 Hz, f or j);
2.08 (d, J=11.9 Hz, f or j); 2.20 (s, 2H, g); 2.25 (s, 2H, h or i);
(s, b.sup.1); 5.96 (s, b 2),
[0082] .sup.13C-NMR (126 MHz): 8.62 (o); 18.27 (a); 29.04 (h or m);
31.39 (m or h); 35.07 (g or i or n); 37.49 (g or i or n); 40.06 (f
or j); 43.90 (j or f); 48.96 (g or i or n); 73.35 (e or k or l);
76.42 (e or k or l); 81.54 (e or k or l); 124.31 (b); 137.85 (c);
166.28 (d)
##STR00014##
[0083] Gas chromatography mass spectroscopy analysis (GC-MS):
[0084] EI 291 (M.sup.+-CH.sub.3, 0.05%), 219
(M.sup.+-C.sub.5H.sub.11O, 100%), 133 (25.6%), 69 (98.6%), 41
(26.1%)
Example 2
Production of Adamantane Derivative (I)
[0085] Synthesis of 3-(2-hydroxyethoxy)-1-adamantyl methacrylate
represented by the following structural formula:
##STR00015##
[0086] (1) Sulfonylating Step
[0087] 3-methanesulfonyloxy-1-adamantyl methacrylate obtained in
the same manner as in the sulfonylating step of Example 1 was added
with 100 ml of diethyl ether, and the temperature of the mixture
was cooled to 0.degree. C., followed by recrystallization. As a
result, 115.13 g of a white solid were obtained. Gas chromatography
analysis and GPC analysis confirmed that
3-methanesulfonyloxy-1-adamantyl methacrylate was obtained at a
purity of 99.1% (GC) or 98.9% (GPC).
[0088] (2) Etherifying Step
[0089] A 2-L glass reactor was equipped with a stirring device. The
product obtained in the above item (1) was loaded into the reactor.
1,100.0 ml (19.725 mmol) of dry ethylene glycol and 76.0 ml (545
mmol) of dry triethylamine were added to the reactor, and the
mixture was stirred. The temperature of an oil bath was set to
80.degree. C., and heating was performed for 2 hours. Gas
chromatography analysis confirmed that a target product was
obtained at a degree of conversion of 99.9% and a selectivity of
99.8%. The reaction liquid was transferred to a 2-L separating
funnel, and 600 ml of diethyl ether and 200 ml of water were added
to the resultant so that extraction to an organic layer was
performed. 700 ml of 1N dilute hydrochloric acid were added to the
resultant, and the mixture was washed with water. Furthermore, 700
ml of water were added to the resultant, and the mixture was washed
with water, whereby a triethylamine salt was removed. 12.0 g (100
mmol) of anhydrous magnesium sulfate were added to the resultant,
and the whole was dehydrated. After that, magnesium sulfate was
removed by means of filtration. The resultant was evaporated in
such a manner that diethyl ether would be removed, followed by gas
chromatography analysis and GPC analysis. As a result, it was
confirmed that a target product was obtained in a yield of 91.96 g
and at a purity of 99.5% (GC) or 99.4% (GPC). Data on each of
.sup.1H-NMR, .sup.13C-NMR, GC-MS, and a melting point is shown
below.
[0090] Nuclear magnetic resonance analysis (NMR): CDCl.sub.3
[0091] .sup.1H-NMR (500 MHz): 1.52 (d, J=12.8 Hz, 2H); 1.60 (d,
J=12.8 Hz, 2H); 1.70 (d, J=11.3 Hz, 2H); 1.78 (d, J=11.3 Hz, 2H);
1.89 (s, 3H, a); 2.05 (d, J=11.3 Hz, 2H); 2.13 (d, J=11.2 Hz, 2H);
2.17 (s, 2H, g); 2.36 (br-s, 2H); 2.48 (q, J=4.0 Hz, 1H); 3.54 (t,
J=4.6 Hz, 2H, l); 3.68 (q, J=5.0 Hz, 2H, m); 5.49 (q, J=1.5 Hz,
b.sup.1); 5.96 (s, b.sup.2)
[0092] .sup.13C-NMR (127 MHz): 18.18 (a); 30.84 (h); 34.97 (i);
40.04 (f or j); 40.40 (j or f); 45.11 (g); 61.48 (l or m); 62.06 (m
or l); (k); 81.19 (e); 124.54 (b); 137.59 (c); 166.28 (d)
##STR00016##
[0093] Gas chromatography mass spectroscopy analysis (GC-MS):
[0094] EI 281 (M.sup.++1, 0.02%), 280 (M.sup.+, 0.16%), 263
(0.05%), 262 (0.26%), 220 (11.0%), 219 (40.3%), 195 (8.7%), 194
(37.1%), 134 (24.0%), 133 (21.7%), 69 (100%)
[0095] Melting point: DSC
[0096] 50.0 to 54.5.degree. C.
Example 3
Production of Adamantane Derivative (I)
[0097] Synthesis of 3-(2-methoxy)-1-methylethoxy methacrylate
represented by the following structural formula:
##STR00017##
[0098] (1) Sulfonylating Step
[0099] 3-methanesulfonyloxy-1-adamantyl methacrylate was obtained
at a purity of 99.1% (GC) or 98.9% (GPC) in the same manner as in
Example 2.
[0100] (2) Etherifying Step
[0101] A 2-L glass reactor was equipped with a stirring device. The
product obtained in the above item (1) was loaded into the reactor.
1,100.0 ml (11.254 mmol) of dry 1-methoxy-2-propanol and 76.0 ml
(545 mmol) of dry triethylamine were added to the reactor, and the
mixture was stirred. The temperature of an oil bath was set to
80.degree. C., and heating was performed for 2 hours. Gas
chromatography analysis confirmed that a target product was
obtained at a degree of conversion of 99.8% and a selectivity of
99.8%. The reaction liquid was transferred to a 2-L separating
funnel, and 600 ml of diethyl ether and 200 ml of water were added
to the resultant so that extraction to an organic layer was
performed. 700 ml of 1N dilute hydrochloric acid were added to the
resultant, and the mixture was washed with water. Furthermore, 700
ml of water were added to the resultant, and the mixture was washed
with water, whereby a triethylamine salt was removed. 12.0 g (100
mmol) of anhydrous magnesium sulfate were added to the resultant,
and the whole was dehydrated. After that, magnesium sulfate was
removed by means of filtration.
[0102] The resultant was evaporated in such a manner that diethyl
ether would be removed, followed by gas chromatography analysis and
GPC analysis. As a result, it was confirmed that a target product
was obtained in a yield of 106.40 g and at a purity of 99.6% (GC)
or 99.5% (GPC). Data on each of .sup.1H-NMR, .sup.13C-NMR, GC-MS,
and a melting point is shown below.
[0103] Nuclear magnetic resonance analysis (NMR): CDCl.sub.3
[0104] .sup.1H-NMR (500 MHz): 1.21 (o); 1.48 (m, 2H, h or i); 1.80
(br-s, 4H, f or j); 1.85 (s, 3H, a); 1.97 (d, f or j); 2.08 (d, f
or j); (s, 2H, g); 3.24 (s, 3H, p); 3.34 (l); 3.50 (m); 5.43 (s,
b.sup.1); (s, b.sup.2)
[0105] .sup.13C-NMR (127 MHz): 17.7 (o); 18.3 (a); 29.0 (h); 37.5
(g or i); 40.1 (f or j); 43.9 (j or f); 49.0 (g or i); 54.2 (p);
67.9 (l); 75.4 (e or k); 76.42 (e or k); 80.6 (m); 124.3 (b); 137.9
(c); 166.3 (d)
##STR00018##
[0106] Gas chromatography mass spectroscopy analysis (GC-MS):
[0107] EI 263 (M.sup.+-CH.sub.2OCH.sub.3, 11.1%), 220 (16.7%), 219
(100%), 133 (25.3%), (12.2%), 69 (99.4%), 45 (10.4%), 41
(19.9%)
Example 4
Production of Adamantane Derivative (I)
[0108] Synthesis of 3-(2-cyanoethoxy)-1-adamantyl methacrylate
represented by the following structural formula:
##STR00019##
[0109] (1) Sulfonylating Step
[0110] 3-methanesulfonyloxy-1-adamantyl methacrylate was obtained
at a purity of 99.1% (GC) or 98.9% (GPC) in the same manner as in
the Example 2.
[0111] (2) Etherifying Step
[0112] A 2-L glass reactor was equipped with a stirring device. The
product obtained in the above item (1) was loaded into the reactor.
1,100.0 ml (16.110 mmol) of dry 3-hydroxypropionynitrile and 76.0
ml (545 mmol) of dry triethylamine were added to the reactor, and
the mixture was stirred. The temperature of an oil bath was set to
80.degree. C., and heating was performed for 2 hours. Gas
chromatography analysis confirmed that a target product was
obtained at a degree of conversion of 99.8% and a selectivity of
99.8%. The reaction liquid was transferred to a 2-L separating
funnel, and 600 ml of diethyl ether and 200 ml of water were added
to the resultant so that extraction to an organic layer was
performed. 700 ml of 1N dilute hydrochloric acid were added to the
resultant, and the mixture was washed with water. Furthermore, 700
ml of water were added to the resultant, and the mixture was washed
with water, whereby a triethylamine salt was removed. 12.0 g (100
mmol) of anhydrous magnesium sulfate were added to the resultant,
and the whole was dehydrated. After that, magnesium sulfate was
removed by means of filtration.
[0113] The resultant was evaporated in such a manner that diethyl
ether would be removed, followed by gas chromatography analysis and
GPC analysis. As a result, it was confirmed that a target product
was obtained in a yield of 95.9 g and at a purity of 98.5% (GC) or
99.0% (GPC). Data on each of .sup.1H-NMR, .sup.13C-NMR, GC-MS, and
a melting point is shown below.
[0114] Nuclear magnetic resonance analysis (NMR): CDCl.sub.3
[0115] .sup.1H-NMR (500 MHz): 1.48 (m, 2H, h or i); 1.80 (br-s, 4H,
f or j); 1.85 (s, 3H, a); 1.97 (d, f or j); 2.08 (d, f or j); 2.20
(s, 2H, g); 2.58 (m); 3.74 (l); 5.43 (s, b.sup.1); 5.96 (s,
b.sup.2)
[0116] .sup.13C-NMR (127 MHz): 19.6 (m); 18.3 (a); 29.0 (h); 37.5
(g or i); 40.1 (f or j); 43.9 (j or f); 49.0 (g or i); 61.0 (l);
75.4 (e or k); 76.42 (e or k); 117.7 (n); 124.3 (b); 137.9 (c);
166.3 (d)
##STR00020##
[0117] Gas chromatography mass spectroscopy analysis (GC-MS):
[0118] EI 290 (M.sup.++1, 0.18%), 289 (M.sup.+, 1.4%), 204 (43.1%),
203 (100%), (76.9%), 135 (39.3%), 92 (78.3%), 69 (88.6%), 41
(69.9%)
Example 5
Production of Adamantane Derivative (II) Involving Use of Poor
Solvent Upon Separation
[0119] Synthesis of 3-methanesulfonyloxy-1-adamantyl methacrylate
represented by the following structural formula:
##STR00021##
[0120] A 2-L glass reactor was equipped with a stirring device and
a dropping funnel. 118.16 g (500 mmol) of 3-hydroxy-1-adamantyl
methacrylate (ADAMANTATE HM, manufactured by Idemitsu Kosan Co.,
Ltd.), 104.5 ml (750 mmol) of dry triethylamine, and 1 L of dry
tetrahydrofuran were added to the reactor, and the mixture was
stirred while the temperature of the mixture was cooled to
0.degree. C. in an ice bath. 46.4 ml (600 mmol) of methanesulfonyl
chloride were dropped to the mixture over 1 hour, and the whole was
stirred for an additional 1 hour, followed by gas chromatography
analysis. As a result, it was confirmed that 3-hydroxy-1-adamantyl
methacrylate was completely converted and a target product was
obtained at a selectivity of 99.5%. 50 ml of water were added to
the resultant to deactivate unreacted methanesulfonyl chloride, and
tetrahydrofuran was removed by using an evaporator. The resultant
was transferred to a 2-L separating funnel, 600 ml of diethyl ether
and 550 ml of water were added to the resultant twice, the mixture
was washed with water twice, and a triethylamine salt was removed.
After diethyl ether had been removed from the resultant by using an
evaporator, 300 ml of methanol were added to the remainder to
precipitate a polymer, and 31.44 g of the polymer were removed by
means of filtration. After methanol had been removed from the
filtrate by using an evaporator, 200 ml of diethyl ether and 12.0 g
(100 mmol) of anhydrous magnesium sulfate were added to the
resultant, and the whole was dehydrated. After that, magnesium
sulfate was removed by means of filtration. Diethyl ether was
removed from the resultant by using an evaporator, followed by gas
chromatography analysis and GPC analysis. As a result, it was
confirmed that a target product was obtained in a yield of 115.37 g
and at a purity of 98.2% (GC) or 98.7% (GPC). 50 ml of diethyl
ether were added to the resultant, and the temperature of the
mixture was cooled to -20.degree. C., followed by
recrystallization. As a result, 102.21 g of a white solid were
obtained. Gas chromatography analysis confirmed that a target
product was obtained at a purity of 98.9%.
[0121] The analyses of the compound are shown below.
[0122] Nuclear magnetic resonance analysis (NMR): CDCl.sub.3
[0123] .sup.1H-NMR (500 MHz): 1.55 (g); 1.85 (c); 2.04 to 2.06 (f
or i); 2.13 to 2.16 (f or i); 2.18 (h); 2.39 (f or i); 2.58 (f or
i); 2.97 (k); 5.47 to 5.48 (a2); 5.98 (a1)
[0124] .sup.13C-NMR (127 MHz): 18.3 (c); 31.5 (k); 34.3 (f or h or
i); 39.5 (f or h or i); 40.9 (g); 41.7 (f or h or i); 46.6 (f or h
or i); 80.6 (j); 90.3 (e); 125.0 (a); 137.4 (b); 166.2 (d)
[0125] Gas chromatography mass spectroscopy analysis (GC-MS): EI
315 (M.sup.++1, 2.%), 314 (M.sup.+, 11.4%), 149 (78.8%), 133
(82.6%), 69 (100%)
Example 6
Production of Adamantane Derivative (II) Involving Use of Organic
Solvent Having Low Dielectric Constant Upon Reaction
[0126] A 200-mL glass reactor was equipped with a stirring device,
a dropping funnel, and a temperature gauge. 10.0 g (42 mmol) of
ADAMANTATE HM (manufactured by Idemitsu Kosan Co., Ltd.:
3-hydroxy-1-adamantyl methacrylate), 8.8 mL (63 mmol) of
triethylamine, and 84.0 mL of toluene were added to the reactor,
and the mixture was stirred while the reactor was immersed in a
water bath at 25.degree. C. 4.0 mL (50 mmol) of methanesulfonyl
chloride were dropped to the mixture over 35 minutes, and the whole
was stirred for an additional 25 minutes. 10 mL of water were added
to the resultant to deactivate unreacted methanesulfonyl chloride.
Part of the reaction liquid was taken and subjected to GPC
measurement in such a manner that a production ratio between a
target product and a polymer would be measured. The remaining
reaction liquid was transferred to a 200-mL separating funnel, and
the resultant was washed with 40 mL of water added to the
resultant. After that, an organic layer was washed with 50 mL of
1-mmol/mL hydrochloric acid and then with 50 mL of water. No
polymer was precipitated in the course of the liquid separating
operation. 6.0 g (50 mmol) of anhydrous magnesium sulfate were
added to the resultant, and the whole was dehydrated. After that,
magnesium sulfate was removed by means of filtration. The filtrate
was subjected to an evaporator in such a manner that toluene would
be distilled off. After that, the temperature of the resultant
viscous product was cooled to 0.degree. C., followed by
crystallization. After having been washed with a small amount of
n-hexane, the crystal was separated by means of filtration, and was
dried under reduced pressure until the amount of the crystal became
constant, whereby an adamantane derivative as a target product
(3-methanesulfonyloxy-1-adamantyl methacrylate) was obtained. Table
1 shows the results of: the yield (mol %) of the target product
with respect to the adamantane compound as a raw material; the
purity (mass %) of the target product measured by means of gas
chromatography; and the production ratio (mass %) of the polymer as
a result of the GPC measurement.
Example 6-1
Production of Adamantane Derivative (II) not Involving Use of
Organic Solvent Having Low Dielectric Constant Upon Reaction
[0127] A 200-mL glass reactor was equipped with a stirring device,
a dropping funnel, and a temperature gauge. 10.0 g (42 mmol) of
ADAMANTATE HM (manufactured by Idemitsu Kosan Co., Ltd.:
3-hydroxy-1-adamantyl methacrylate), 8.8 mL (63 mmol) of
triethylamine, and 84 mL of tetrahydrofuran were added to the
reactor, and the mixture was stirred while the reactor was immersed
in a water bath at 25.degree. C. 4.0 mL (50 mmol) of
methanesulfonyl chloride were dropped to the mixture over 35
minutes, and the whole was stirred for an additional 25 minutes. 10
mL of water were added to the resultant to deactivate unreacted
methanesulfonyl chloride. Part of the reaction liquid was taken and
subjected to GPC measurement in such a manner that a production
ratio between a target product and a polymer would be measured. The
remaining reaction liquid was transferred to a 300-mL separating
funnel, 100 mL of diethyl ether and 40 mL of water were added to
the resultant, and the mixture was washed with water. At that time,
a polymer was precipitated to adhere to the separating funnel. In
addition, the cock of the separating funnel was clogged with the
polymer upon separation of an organic layer and an aqueous layer,
so liquid separation involved time and a trouble. After that, the
organic layer was washed with 50 mL of 1-mmol/mL hydrochloric acid
and then with 50 mL of water. 6.0 g (50 mmol) of anhydrous
magnesium sulfate were added to the resultant, and the whole was
dehydrated. After that, magnesium sulfate was removed by means of
filtration. The filtrate was subjected to an evaporator in such a
manner that the solvent would be distilled off. After that, the
temperature of the resultant viscous product was cooled to
0.degree. C., followed by crystallization. After having been washed
with a small amount of n-hexane, the crystal was separated by means
of filtration, and was dried under reduced pressure until the
amount of the crystal became constant, whereby a target product was
obtained. Table 1 shows the results of: the yield of the target
product; the purity of the target product measured by means of gas
chromatography; and the production ratio of the polymer as a result
of the GPC measurement.
Example 7
Production of Adamantane Derivative (II) Involving Use of Organic
Solvent Having Low Dielectric Constant Upon Reaction
[0128] A 200-mL glass reactor was equipped with a stirring device,
a dropping funnel, and a temperature gauge. 10.0 g (42 mmol) of
ADAMANTATE HM (manufactured by Idemitsu Kosan Co., Ltd.:
3-hydroxy-1-adamantyl methacrylate), 8.8 mL (63 mmol) of
triethylamine, and 42 mL of toluene were added to the reactor, and
the mixture was stirred while the temperature of the mixture was
cooled to 5.degree. C. in an ice bath. 4.0 mL (50 mmol) of
methanesulfonyl chloride were dropped to the mixture over 3
minutes, and the whole was stirred for an additional 5 minutes. 10
mL of water were added to the resultant to deactivate unreacted
methanesulfonyl chloride. Part of the reaction liquid was taken and
subjected to GPC measurement in such a manner that a production
ratio between a target product and a polymer would be measured. The
remaining reaction liquid was transferred to a 200-mL separating
funnel, and the resultant was washed with 40 mL of water added to
the resultant. After that, an organic layer was washed with 50 mL
of 1-mmol/mL hydrochloric acid and then with 50 mL of water. No
polymer was precipitated in the course of the liquid separating
operation. 6.0 g (50 mmol) of anhydrous magnesium sulfate were
added to the resultant, and the whole was dehydrated. After that,
magnesium sulfate was removed by means of filtration. The filtrate
was subjected to an evaporator in such a manner that toluene would
be distilled off. After that, the temperature of the resultant
viscous product was cooled to 0.degree. C., followed by
crystallization. After having been washed with a small amount of
n-hexane, the crystal was separated by means of filtration, and was
dried under reduced pressure until the amount of the crystal became
constant, whereby a target product was obtained. Table 1 shows the
results of: the yield (mol %) of the target product with respect to
the adamantane compound as a raw material; the purity (mass %) of
the target product measured by means of gas chromatography; and the
production ratio (mass %) of the polymer as a result of the GPC
measurement.
Example 7-1
Production of Adamantane Derivative (II) not Involving Use of
Organic Solvent Having Low Dielectric Constant Upon Reaction
[0129] A 200-mL glass reactor was equipped with a stirring device,
a dropping funnel, and a temperature gauge. 10.0 g (42 mmol) of
ADAMANTATE HM (manufactured by Idemitsu Kosan Co., Ltd.:
3-hydroxy-1-adamantyl methacrylate), 8.8 mL (63 mmol) of
triethylamine, and 42 mL of tetrahydrofuran were added to the
reactor, and the mixture was stirred while the temperature of the
mixture was cooled to 5.degree. C. in an ice bath. 4.0 mL (50 mmol)
of methanesulfonyl chloride were dropped to the mixture over 3
minutes, and the whole was stirred for an additional 5 minutes. 10
mL of water were added to the resultant to deactivate unreacted
methanesulfonyl chloride. Part of the reaction liquid was taken and
subjected to GPC measurement in such a manner that a production
ratio between a target product and a polymer would be measured. The
remaining reaction liquid was transferred to a 300-mL separating
funnel, 100 mL of diethyl ether and 40 mL of water were added to
the resultant, and the mixture was washed with water. At that time,
a polymer was precipitated to adhere to the separating funnel.
After that, the organic layer was washed with 50 mL of 1-mmol/mL
hydrochloric acid and then with 50 mL of water. 6.0 g (50 mmol) of
anhydrous magnesium sulfate were added to the resultant, and the
whole was dehydrated. After that, magnesium sulfate was removed by
means of filtration. The filtrate was subjected to an evaporator in
such a manner that the solvent would be distilled off. After that,
the temperature of the resultant viscous product was cooled to
0.degree. C., followed by crystallization. After having been washed
with a small amount of n-hexane, the crystal was separated by means
of filtration, and was dried under reduced pressure until the
amount of the crystal became constant, whereby a target product was
obtained. Table 1 shows the results of: the yield of the target
product; the purity of the target product measured by means of gas
chromatography; and the production ratio of the polymer as a result
of the GPC measurement.
Example 7-2
Production of Adamantane Derivative (II) not Involving Use of
Organic Solvent Having Low Dielectric Constant Upon Reaction
[0130] A target product was obtained in the same manner as in
Example 7 except that toluene in Example 7 was changed to methylene
chloride. A polymer was precipitated in the course of liquid
separation. Table 1 shows the results of: the yield of the target
product; the purity of the target product measured by means of gas
chromatography; and the production ratio of the polymer as a result
of the GPC measurement.
Example 8
Production of Adamantane Derivative (II) Involving Use of Organic
Solvent Having Low Dielectric Constant Upon Reaction
[0131] A target product was obtained in the same manner as in
Example 7 except that the amount of toluene, which had been 42 mL
in Example 7, was changed to 84 mL. No polymer was precipitated in
the course of liquid separation. Table 1 shows the results of: the
yield of the target product; the purity of the target product
measured by means of gas chromatography; and the production ratio
of the polymer as a result of the GPC measurement.
Example 9
Production of Adamantane Derivative (II) Involving Use of Organic
Solvent Having Low Dielectric Constant Upon Reaction
[0132] A target product was obtained in the same manner as in
Example 7 except that the amount of toluene was changed to ethylene
acetate. No polymer was precipitated in the course of liquid
separation. Table 1 shows the results of: the yield of the target
product; the purity of the target product measured by means of gas
chromatography; and the production ratio of the polymer as a result
of the GPC measurement.
Example 10
Production of Adamantane Derivative (II) Involving Use of Organic
Solvent Having Low Dielectric Constant Upon Reaction
[0133] A target product was obtained in the same manner as in
Example 7 except that the amount of toluene was changed to a mixed
solvent with 22 mL of cyclohexane and 22 mL of tetrahydrofuran. No
polymer was precipitated in the course of liquid separation. Table
1 shows the results of: the yield of the target product; the purity
of the target product measured by means of gas chromatography; and
the production ratio of the polymer as a result of the GPC
measurement.
TABLE-US-00001 TABLE 1 Example Example Example Example Example
Example Example Example 6 6-1 7 7-1 7-2 8 9 10 Solvent usage (mL)
Toluene 84 42 84 Cyclohexane 22 Ethyl acetate 42 Tetrahydrofuran 84
42 22 Methylene chloride 42 Dielectric constant of 2.2 8.2 2.2 8.2
9.1 2.2 6.0 5.1 solvent Reaction method Bath temperature (.degree.
C.) 25 25 5 5 5 5 5 5 Drop time (min) 35 35 3 3 3 3 3 3 Time for
subsequent 25 25 5 5 5 5 5 5 stirring (min) Adamantane derivative
(II) Yield (mol %) 95 66 94 90 86 96 95 95 Purity (mass %) 99.0
98.3 99.1 97.7 94.8 99.4 98.9 98.9 Production ratio of 0.4 28.8 0.6
4.4 8.3 0.3 2.2 1.9 polymer
INDUSTRIAL APPLICABILITY
[0134] Each of the adamantane derivative (I) of the present
invention represented by the general formula (I) and the adamantane
derivative (II) of the present invention represented by the general
formula (II) is a novel adamantyl (meth)acrylate compound, and is
useful as a monomer for a functional resin such as a photosensitive
resin in the field of photolithography.
[0135] The adamantane derivative (I) of the present invention is
expected to exert an alleviating effect on surface roughness after
exposure (LER: irregularities appearing on the side surface of a
resist, LWR: waviness when wiring is seen from directly above) and
an improving effect on, for example, the temperature dependence of
PEB (a heat treatment for diffusing an acid generated by
exposure).
[0136] In addition, compatibility between the adamantane derivative
(II) of the present invention and a photoacid generator (PAG) as
one component of a resist agent mixed liquid is considered to
improve. As a result, a uniform film can be formed, and the film is
expected to exert an alleviating effect on surface roughness after
exposure (LER: irregularities appearing on the side surface of a
resist, LWR: waviness when wiring is seen from directly above).
[0137] Furthermore, each of the adamantane derivative (I) and the
adamantane derivative (II) can be produced in high yield by means
of the process for producing each of those adamantane derivatives
of the present invention. In particular, in the process for
producing the adamantane derivative (II) involving a reaction in an
organic solvent having a dielectric constant at 20.degree. C. of 8
or less, the production of a polymer can be suppressed, so an
improvement in handleability is achieved, and the derivative can be
produced efficiently and industrially advantageously.
* * * * *