Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2003-05-14
2003-12-23
Morris, Patricia L. (Department: 1625)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
active
06667402
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to a process for producing &ohgr;-mercaptoalkylpyridine.
PRIOR ART
&ohgr;-Mercaptoalkylpyridine such as 2-(2-mercaptoethyl)pyridine, 4-(2-mercaptoethyl)pyridine and the like are industrially useful compounds as an additive of chelating catalysts for producing bisphenol A; intermediates for medical supplies or agricultural chemicals; and the like.
Conventionally, as the method for producing &ohgr;-mercaptoalkylpyridines, there is reported, for example, a method of reacting 2-vinylpyridine with hydrogen sulfide to produce 2-(2-mercaptoethyl)pyridine in a yield of 23% (P. S. K. Chia et al., Aust. J. Chem., 19, 1835 (1966) and R. B. Thompson et al., Industrial and Engineering Chemistry, 44, 1659 (1952)).
An object of the present invention is to provide a process for producing &ohgr;-mercaptoalkylpyridines in high yield even if industrially easily available hydrogen sulfide is used.
SUMMARY OF THE INVENTION
The present invention relates to the followings.
<1> A process for producing &ohgr;-mercaptoalkylpyridine of the formula (II)
wherein R
1
and R
2
each independently represent hydrogen or methyl, and
n represents an integer of 0 to 2,
comprising reacting pyridine compound of the formula (I)
wherein R
1
, R
2
and n have the same meanings described above, and hydrogen sulfide in the presence of tertiary amine, which is hereinafter referred to as “the present process”.
<2> The process according to <1> wherein the tertiary amine is at least one tertiary amine compound selected from the group consisting of the following (A) to (C):
wherein R
21
, R
22
and R
23
each independently represent alkyl having 1 to 8 carbon atoms, cycloalkyl having 4 to 12 carbon atoms or aromatic hydrocarbon group having 6 to 12 carbon atoms and at least one hydrogen on the alkyl, cycloalkyl or aromatic hydrocarbon group may be substituted by amino, N-alkylamino having 1 to 8 carbon atoms, N,N-diakylamino having 2 to 16 carbon atoms or hydroxy.
wherein R
24
represents alkyl having 1 to 8 carbon atoms, cycloalkyl having 4 to 12 carbon atoms or aromatic hydrocarbon group having 6 to 12 carbon atoms, m represents an integer of 0 to 8, and at least one hydrogen atom on —CH
2
— constituting a ring or on R
24
may be substituted by amino group, N-alkylamino group having 1 to 8 carbon atoms, N,N-dialkylamino group having 2 to 16 carbon atoms or hydroxyl and one or two —CH
2
— constituting a ring may be substituted by —NH— or —O—.
(C): Aromatic nitrogen-containing heterocyclic compound wherein at least one hydrogen may be substituted by alkyl having 1 to 8 carbon atoms and at least one hydrogen on the alkyl may be substitutede by amino, N-alkylamino having 1 to 8 carbon atoms or N,N-dialkylamino having 2 to 16 carbon atoms.
<3> The process according to <1> or <2> wherein the pyridine compound of the formula (I) is at least one kind selected from the group consisting of 4-vinylpyridine and 2-vinylpydirine.
<4> The process according to any one of <1> to <3> wherein the tertiary amine is at least one compound selected from the group consisting of tertiary amine of the following formula (1), tertiary amine of the following formula (2), tertiary amine of the following formula (5) and tertiary amine of the following formula (6):
Tertiary amine of the formula (1)
wherein R
3
to R
1
each independently represent alkyl having 1 to 8 carbon atoms or cycloalkyl having 4 to 12 carbon atoms.
Tertiary amine of the formula (2)
wherein R
6
to R
9
each independently represent alkyl having 1 to 8 carbon atoms or a cycloalkyl having 4 to 12 carbon atoms, p represents an integer of 1 to 8.
Tertiary amine of the formula (5)
wherein R
13
and R
14
each independently represent alkyl having 1 to 8 carbon atoms or cycloalkyl having 4 to 12 carbon atoms, and &phgr;
1
represents aromatic hydrocarbon group.
Tertiary amine of the formula (6)
wherein R
15
represents alkyl having 1 to 8 carbon atoms or cycloalkyl having 4 to 12 carbon atoms, and &phgr;
2
and &phgr;
3
each independently represent aromatic hydrocarbon group.
<5> The process according to any one of <1> to <4> wherein tertiary amine and pyridine (I) are sequentially mixed with hydrogen sulfide previously filled in a reaction.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention will be illustrated in detail below.
In the pyridine compound of the formula (I), which is hereinafter referred to as “pyridine (I)”, the compound wherein n is 0 is preferable, and pyridine (I) in which both of R
1
and R
2
represent hydrogen and n is 0 is particularly preferable, and among others, 2-vinylpyridine and 4-vinylpyridine are suitable.
Polymerization inhibitors such as hydroquinones, catechols and the like may be contained usually in an amount of about 0.01 to 0.5% by weight based on pyridine (I), which is sometimes added for deterioration inhibitor of pyridine (I) when stored. It is however recommended that pyridine (I) is purified by simple distillation before the present process.
As hydrogen sulfide used in the present process, that in the form of solution which is dissolved in a solvent such as water, carbon disulfide, methylene chloride and the like may be used, and usually, commercially available compressed hydrogen sulfide contained in a cylinder, gaseous hydrogen sulfide produced, for example, in a factory, and the like, are used as they are. As the specific hydrogen sulfide use method, there are exemplified a method in which hydrogen sulfide is previously introduced into a reaction vessel, then, pyridine (I) and tertiary amine are mixed; a method in which hydrogen sulfide is blown through an introduction tube or the like into a reaction vessel containing mixture of pyridine (I) and tertiary amine; a method in which pyridine (I), tertiary amine and hydrogen sulfide are introduced into a reaction vessel, and the like. For performing the reaction efficiently in use of hydrogen sulfide, the reaction vessel may be sealed, or if necessary, may be pressurized.
The amount of hydrogen sulfide is usually more than 1 mol per 1 mol of pyridine (I), and from the economical standpoint, preferably less than 30 mol. When the reaction is conducted in a sealed vessel, the amount of hydrogen sulfide is usually more than 1 mol per 1 mol of pyridine (I), and from the economical standpoint, preferably less than 10 mol.
The tertiary amine used in the present invention is an amine compound having a nitrogen atom whose three bonds connect with carbon atoms.
Preferred examples of the tertiary amine include at least one organic amine compound selected from the group consisting of the following (A) to (C).
(A): Amine comppund of the formula (a)
wherein R
21
, R
22
and R
23
each independently represent alkyl having 1 to 8 carbon atoms, cycloalkyl having 4 to 12 carbon atoms or aromatic hydrocarbon group having 6 to 12 carbon atoms and at least one hydrogen on the alkyl, cycloalkyl or aromatic hydrocarbon group may be substituted by amino, N-alkylamino having 1 to 8 carbon atoms, N,N-dialkylamino having 2 to 16 carbon atoms or hydroxy.
(B): Alicyclic amine of the formula (b)
wherein R
24
represents alkyl having 1 to 8 carbon atoms, cycloalkyl having 4 to 12 carbon atoms or aromatic hydrocarbon group having 6 to 12 carbon atoms, m represents an integer of 0 to 8, at least one hydrogen atom on —CH
2
— constituting a ring or on R
24
may be substituted by amino group, N-alkylamino group having 1 to 8 carbon atoms, N,N-dialkylamino group having 2 to 16 carbon atoms or hydroxyl, and one or two —CH
2
— constituting a ring may be substituted by —NH— or —O—.
(C): Aromatic nitrogen-containing heterocyclic compound wherein at least one hydrogen may be substituted by alkyl having 1 to 8 carbon atoms and at least one hydrogen on the alkyl may be substitutede by amino, N-alkylamino having 1 to 8 carbon atoms or N,N-dialkylamino having 2 to 16 carbon atoms.
Examples of alkyl group having 1 to 8 carbon atoms in (A), (B) or (C) include methyl, ethyl, butyl and the like.
Fukuda Nobuyasu
Fukui Yasuhiro
Sato Yoshinobu
Morris Patricia L.
Sumitomo Chemical Company Limited
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