JP7096686B2 - A method for producing an organolithium compound having an amino group and an intermediate thereof, and a method for producing a conjugated diene-based polymer using the organolithium compound. - Google Patents

Description

The present invention relates to a method for producing an organolithium compound having an amino group and an intermediate thereof, and a method for producing a conjugated diene-based polymer using the organolithium compound.

Organic lithium compounds with amino groups are capable of synthesizing physiologically active substances (eg, pharmaceuticals, pesticides), functional materials (eg, liquid crystal materials, electronic materials, optical materials, resins, dyes or their intermediates). It is a raw material. In particular, when an organic lithium compound having an amino group is used as a polymerization initiator, an amino group can be introduced into the terminal of the obtained polymer, which is very useful in the development of a polymer material.

As a method for producing an organolithium compound having an amino group, for example, Patent Document 1 describes a method of reacting 3-chloro-N, N-dimethylpropylamine with metallic lithium under heating conditions.

US 5,527,753

In the method described in Patent Document 1, metallic lithium, which is difficult to handle, must be used in excess. Further, in the method described in Patent Document 1, activation of metallic lithium in a high temperature and argon atmosphere must be carried out for a long time before using metallic lithium in the reaction, and this method is easily carried out on a commercial scale. Can not. Further, in the method of Patent Document 1, since a chlorine compound having low reactivity and metallic lithium are reacted under heating conditions, a large amount of by-products (for example, amine) is produced, and the yield and purity of the obtained organic lithium compound are increased. descend. The by-produced amine is a coordinating compound and may coordinate with the organolithium compound to reduce the stability of the organolithium compound. In addition, by-products such as amines may adversely affect the obtained polymer, for example, when an organolithium compound is used as a polymerization initiator.

The present invention has been made in view of the above circumstances, and an object thereof is to provide a method capable of producing an organic lithium compound having an amino group under industrially advantageous conditions without using metallic lithium. To do.

The present invention that can achieve the above object is as follows.
[1] A step (a) of reacting a salt represented by the formula (1) with an alkali metal iodide represented by the formula (2) to obtain a salt represented by the formula (3).
Step (b), a step (b) of reacting a salt represented by the formula (3) with a base to obtain a compound represented by the formula (4).
The step (c) and the formula (6) of reacting the compound represented by the formula (4) with the organolithium compound represented by the formula (5) to obtain the organolithium compound represented by the formula (6). 2. The step (d) of reacting an organolithium compound represented by the formula (7) with a compound having an olefinic double bond represented by the formula (7) to obtain an organolithium compound represented by the formula (8) is included. A method for producing an organolithium compound represented by the formula (8).

(During the ceremony,
A ¹ and A ² independently have a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, and a silyl which may have a substituent. Represents a siroxy group which may have a group or a substituent, or a nitrogen-containing heterocyclic group which may have a substituent together with a nitrogen atom to which A ¹ and A ² are bonded and adjacent to them. Form.
Z represents a divalent aliphatic hydrocarbon group which may have a substituent.
X represents a chlorine atom or a bromine atom.
HB represents an acid.
M represents an alkali metal atom.
R represents a hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent.
^Q1 represents a compound having an olefinic double bond.
Q ² represents a structural unit derived from Q ¹ .
n represents 1 to 20. )

[2] In the step (a), it is represented by the formula (1) in the presence of 0.5 to 5 mol of the polar solvent with respect to 1 mol of the salt represented by the formula (1) in the hydrocarbon solvent. The method according to the above [1], wherein the salt is reacted with the alkali metal iodide represented by the formula (2).

[3] A step (b) of reacting a salt represented by the formula (3) with a base to obtain a compound represented by the formula (4).
The step (c) and the formula (6) of reacting the compound represented by the formula (4) with the organolithium compound represented by the formula (5) to obtain the organolithium compound represented by the formula (6). 2. The step (d) of reacting an organolithium compound represented by the formula (7) with a compound having an olefinic double bond represented by the formula (7) to obtain an organolithium compound represented by the formula (8) is included. A method for producing an organolithium compound represented by the formula (8).

(During the ceremony,
A ¹ and A ² independently have a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, and a silyl which may have a substituent. Represents a siroxy group which may have a group or a substituent, or a nitrogen-containing heterocyclic group which may have a substituent together with a nitrogen atom to which A ¹ and A ² are bonded and adjacent to them. Form.
Z represents a divalent aliphatic hydrocarbon group which may have a substituent.
HB represents an acid.
R represents a hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent.
^Q1 represents a compound having an olefinic double bond.
Q ² represents a structural unit derived from Q ¹ .
n represents 1 to 20. )

[4] The step (c) of reacting the compound represented by the formula (4) with the organolithium compound represented by the formula (5) to obtain the organolithium compound represented by the formula (6), and the formula. Step (d) of reacting the organolithium compound represented by (6) with the compound having an olefinic double bond represented by the formula (7) to obtain the organolithium compound represented by the formula (8). :
A method for producing an organic lithium compound represented by the formula (8).

(During the ceremony,
A ¹ and A ² independently have a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, and a silyl which may have a substituent. Represents a siroxy group which may have a group or a substituent, or a nitrogen-containing heterocyclic group which may have a substituent together with a nitrogen atom to which A ¹ and A ² are bonded and adjacent to them. Form.
Z represents a divalent aliphatic hydrocarbon group which may have a substituent.
R represents a hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent.
^Q1 represents a compound having an olefinic double bond.
Q ² represents a structural unit derived from Q ¹ .
n represents 1 to 20. )

[5] The method according to any one of the above [1] to [4], wherein the compound having an olefinic double bond is a diene compound.

[6] The step of producing the organolithium compound represented by the formula (8) by the method according to any one of the above [1] to [5], and the organic lithium compound represented by the formula (8). A method for producing a conjugated diene-based polymer, which comprises a step of polymerizing a conjugated diene compound in the presence of the compound.

[7] The salt represented by the formula (1) and the salt represented by the formula (2) in the presence of 0.5 to 5 mol of the polar solvent with respect to 1 mol of the salt represented by the formula (1) in the hydrocarbon solvent. The step (a) of reacting with the alkali metal iodide represented by the formula (3) to obtain the salt represented by the formula (3), and the reaction of the salt represented by the formula (3) with the base, the formula ( Step (b) to obtain the compound represented by 4)
A method for producing a compound represented by the formula (4), which comprises.

(During the ceremony,
A ¹ and A ² independently have a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, and a silyl which may have a substituent. Represents a siroxy group which may have a group or a substituent, or a nitrogen-containing heterocyclic group which may have a substituent together with a nitrogen atom to which A ¹ and A ² are bonded and adjacent to them. Form.
Z represents a divalent aliphatic hydrocarbon group which may have a substituent.
X represents a chlorine atom or a bromine atom.
HB represents an acid.
M represents an alkali metal atom. )

[8] The salt represented by the formula (1) and the salt represented by the formula (2) in the presence of 0.5 to 5 mol of the polar solvent with respect to 1 mol of the salt represented by the formula (1) in the hydrocarbon solvent. A method for producing a salt represented by the formula (3), which comprises a step (a) of reacting with an alkali metal iodide represented by the formula (3) to obtain a salt represented by the formula (3).

(During the ceremony,
A ¹ and A ² independently have a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, and a silyl which may have a substituent. Represents a siroxy group which may have a group or a substituent, or a nitrogen-containing heterocyclic group which may have a substituent together with a nitrogen atom to which A ¹ and A ² are bonded and adjacent to them. Form.
Z represents a divalent aliphatic hydrocarbon group which may have a substituent.
X represents a chlorine atom or a bromine atom.
HB represents an acid.
M represents an alkali metal atom. )

[9] The method according to the above [2], [7] or [8], wherein the amount of the hydrocarbon solvent is 0.5 to 25 parts by weight with respect to 1 part by weight of the salt represented by the formula (1). ..

According to the present invention, an organolithium compound having an amino group can be produced under industrially advantageous conditions.

<Definition>
First, the definitions of the basics and the like in the present specification will be described in order.
“C _xy ” means that the number of carbon atoms is x or more and y or less (x and y represent numbers).

Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium. Of these, sodium, potassium, rubidium, and cesium are preferable, and sodium and potassium are more preferable.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The hydrocarbon group preferably has 1 to 24 carbon atoms. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group and an aralkyl group.

The alkyl group may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 24, more preferably 1 to 10, and even more preferably 1 to 6. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and a 1-ethylpropyl group. Hexyl group, isohexyl group, 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, Examples thereof include a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecil group, an icosyl group, an eicosyl group, a henicosyl group, a heneicosyl group, a docosyl group, a tricosyl group and a tetracosyl group.

The alkenyl group may be linear or branched. The alkenyl group has preferably 2 to 24 carbon atoms, more preferably 2 to 10 carbon atoms, and more preferably 2 to 6 carbon atoms. Examples of the alkenyl group include an ethenyl group (that is, a vinyl group), a 1-propenyl group, a 2-propenyl group, a 2-methyl-1-propenyl group, a 1-butenyl group, a 2-butenyl group and a 3-butenyl group. 1-Methyl-1-propenyl group, 1-methyl-2-propenyl group, 2-methyl-1-propenyl group, 2-methyl-2-propenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group , 4-Pentenyl group, 1-methyl-1-butenyl group, 2-methyl-1-butenyl group, 3-methyl-1-butenyl group, 1-methyl-2-butenyl group, 2-methyl-2-butenyl group , 3-Methyl-2-butenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-1-pentenyl group, 2-methyl-1- Penthenyl group, 4-methyl-3-pentenyl group, 2-ethyl-1-butenyl group, 2-heptenyl group, 2-octenyl group, 2-nonenyl group, 2-decenyl group, 2-undecenyl group, 2-dodecenyl group , 2-Tridecenyl group, 2-Tetradecenyl group, 2-Pentadecenyl group, 2-Hexadecenyl group, 2-Heptadesenyl group, 2-Octadecenyl group, 2-Nonadecenyl group, 2-Icosenyl group, 2-Eicosenyl group, 2-Henicosenyl group , 2-heneicosenyl group, 2-docosenyl group, 2-tricosenyl group, 2-tetracosenyl group and the like.

The alkynyl group may be linear or branched. The alkynyl group has preferably 2 to 24 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 6 carbon atoms. Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-methyl-2-propynyl group, a 1-pentynyl group, and 2 -Pentynyl group, 3-pentynyl group, 4-pentynyl group, 1-methyl-3-butynyl group, 2-methyl-3-butynyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 4-hexynyl Group, 5-hexynyl group, 2-heptynyl group, 2-octynyl group, 2-noninyl group, 2-decynyl group, 2-undecynyl group, 2-dodecynyl group, 2-tridecynyl group, 2-tetradecynyl group, 2-pentadecynyl Group, 2-hexadecynyl group, 2-heptadecynyl group, 2-octadecinyl group, 2-nonadecinyl group, 2-icocinyl group, 2-eicocinyl group, 2-henicocinyl group, 2-heneicocinyl group, 2-docosine group, 2-tricocynyl Examples include a group and a 2-tetracosinyl group.

The cycloalkyl group has preferably 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms. Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a bicyclo [2.2.1] heptyl group, and a bicyclo [2.2.2] octyl group. , Bicyclo [3.2.1] octyl group, adamantyl group and the like.

The cycloalkenyl group has preferably 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms. Examples of the cycloalkenyl group include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group, a cycloheptenyl group, and a cyclooctenyl group.

The aryl group preferably has 6 to 18 carbon atoms, and more preferably 6 to 14 carbon atoms. Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group and a 9-anthryl group.

The carbon number of the aralkyl group is preferably 7 to 20, more preferably 7 to 16. Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group and a phenylpropyl group.

A description of the alkyl group, which is part of the alkoxy group (ie, the alkyloxy group), is as described above. The same applies to the description of the alkyl group which is a part of the group described later. Preferable examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group and a hexyloxy group.

The description of the cycloalkyl group, which is part of the cycloalkyloxy group, is as described above. The same applies to the description of the cycloalkyl group which is a part of the group described later. Preferable examples of the cycloalkyloxy group include a cyclopropyloxy group, a cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group and a cyclooctyloxy group.

The description of the aryl group, which is part of the aryloxy group, is as described above. The same applies to the description of the aryl group, which is a part of the group described later. Preferable examples of the aryloxy group include a phenyloxy group, a 1-naphthyloxy group and a 2-naphthyloxy group.

The description of the aralkyl group, which is part of the aralkyloxy group, is as described above. The same applies to the description of the aralkyl group, which is a part of the group described later. Preferable examples of the aralkyloxy group include a benzyloxy group, a phenethyloxy group, a naphthylmethyloxy group and a phenylpropyloxy group.

Preferable examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, a sec-butylthio group, a tert-butylthio group, a pentylthio group and a hexylthio group.

Preferable examples of the cycloalkylthio group include a cyclopentylthio group, a cyclohexylthio group and a cycloheptylthio group.

Preferable examples of the arylthio group include a phenylthio group and a naphthylthio group.
Preferable examples of the aralkylthio group include a benzylthio group and a phenethylthio group.

Preferable examples of the alkyl-carbonyl group are acetyl group, propanoyl group, butanoyl group, 2-methylpropanol group, pentanoyl group, 3-methylbutanoyl group, 2-methylbutanoyl group, 2,2-dimethylpropa. Examples thereof include a noyl group, a hexanoyl group and a heptanoyle group.

Preferable examples of the aryl-carbonyl group include a benzoyl group, a 1-naphthoyl group and a 2-naphthoyl group.

Preferable examples of the aralkyl-carbonyl group include a phenylacetyl group and a phenylpropionyl group.

Preferable examples of the heterocyclic carbonyl group include a nicotinoyyl group, an isonicotinoyyl group, a tenoyl group, a floyl group, a morpholinylcarbonyl group, a piperidinylcarbonyl group and a pyrrolidinylcarbonyl group.

Suitable examples of alkoxy-carbonyl groups include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, pentyl. Examples thereof include an oxycarbonyl group and a hexyloxycarbonyl group.

Examples of the carbamoyl group which may have a substituent include a carbamoyl group which may have one or two substituents selected from an alkyl group, a cycloalkyl group, an aryl group and an aralkyl group. Be done. Preferable examples of a carbamoyl group which may have a substituent are a carbamoyl group, a mono- or di-alkyl-carbamoyl group (eg, a methylcarbamoyl group, an ethylcarbamoyl group, a dimethylcarbamoyl group, a diethylcarbamoyl group, N. -Ethyl-N-methylcarbamoyl group), mono- or di-cycloalkyl-carbamoyl group (eg, cyclopropylcarbamoyl group, cyclohexylcarbamoyl group), mono- or di-aryl-carbamoyl group (eg, phenylcarbamoyl group), Examples include mono- or di-aralkyl-carbamoyl groups (eg, benzylcarbamoyl group, phenethylcarbamoyl group).

Examples of the amino group which may have a substituent include an alkyl group, an aryl group, an alkyl-carbonyl group, an aryl-carbonyl group, an aralkyl-carbonyl group, a heterocyclic carbonyl group, an alkoxy-carbonyl group and a heterocyclic group. , Carbamoyl group, mono- or di-alkyl-carbamoyl group, mono- or di-aralkyl-carbamoyl group, alkylsulfonyl group and amino group which may have 1 or 2 substituents selected from arylsulfonyl groups. Can be mentioned.

Suitable examples of an amino group which may have a substituent are an amino group, a mono- or di- (may be halogenated alkyl) amino group (eg, a methylamino group, a trifluoromethylamino group). , Dimethylamino group, ethylamino group, diethylamino group, propylamino group, dibutylamino group), mono- or di-cycloalkylamino group (eg cyclopropylamino group, cyclohexylamino group), mono- or di-arylamino Group (eg, phenylamino group), mono- or di-aralkylamino group (eg, benzylamino group, dibenzylamino group), mono- or di-alkyl-carbonylamino group (eg, acetylamino group, propionylamino group) ), Mono- or di-aryl-carbonylamino group (eg, benzoylamino group), mono- or di-aralkyl-carbonylamino group (eg, benzylcarbonylamino group), mono- or di-heterocyclic carbonylamino group (eg) Examples, nicotinoyylamino group, isonicotinoylamino group, piperidinylcarbonylamino group), mono- or di-alkoxy-carbonylamino group (eg, tert-butoxycarbonylamino group), heterocyclic amino group (eg, pyridylamino). Group), carbamoylamino group, (mono- or di-alkyl-carbamoyl) amino group (eg, methylcarbamoylamino group), (mono- or di-aralkyl-carbamoyl) amino group (eg, benzylcarbamoylamino group), alkyl Sulfonylamino group (eg, methylsulfonylamino group, ethylsulfonylamino group), arylsulfonylamino group (eg, phenylsulfonylamino group), (alkyl) (alkyl-carbonyl) amino group (eg, N-acetyl-N-methyl) Amino group), (alkyl) (aryl-carbonyl) amino group (eg, N-benzoyl-N-methylamino group).

The number of ring-constituting atoms of the heterocyclic group is preferably 3 to 14. That is, the heterocyclic group is preferably a 3- to 14-membered heterocyclic group. Examples of the heterocyclic group include (i) an aromatic heterocyclic group containing 1 to 4 heteroatoms selected from a nitrogen atom, a sulfur atom and an oxygen atom in addition to a carbon atom as a ring-constituting atom, and (i) an aromatic heterocyclic group. ii) Examples include non-aromatic heterocyclic groups.

The aromatic heterocyclic group includes, for example, 5 to 14 members (preferably 5 to 10 members) containing 1 to 4 heteroatoms selected from a nitrogen atom, a sulfur atom and an oxygen atom in addition to a carbon atom as a ring-constituting atom. ) Fragrant heterocyclic group.

Suitable examples of aromatic heterocyclic groups include:
Thienyl group, frill group, pyrrolyl group, imidazolyl group, pyrazolyl group, thiazolyl group, isothiazolyl group, oxazolyl group, isooxazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, 1,2,4-oxadiazolinyl group, 1, 5- to 6-membered monocyclic aromatic heterocyclic groups such as 3,4-oxadiazolyl group, 1,2,4-thiadiazolyl group, 1,3,4-thiadiazolyl group, triazolyl group, tetrazolyl group, triazinyl group;
Benzothiophenyl group, benzofuranyl group, benzoimidazolyl group, benzoxazolyl group, benzoisoxazolyl group, benzothiazolyl group, benzoisothiazolyl group, benzotriazolyl group, imidazolepyridinyl group, thienopyridinyl group, flopyridinyl group , Pyrrolopyridinyl group, pyrazolopyridinyl group, oxazolopyridinyl group, thiazolopyridinyl group, imidazopyrazinyl group, imidazopyrimidinyl group, thienopyrimidinyl group, flopyrimidinyl group, pyrrolopyrimidinyl group, pyrazolopyrimidinyl Group, oxazolopyrimidinyl group, thiazolopyrimidinyl group, pyrazorotriadinyl group, naphtho [2,3-b] thienyl group, phenoxatyynyl group, indolyl group, isoindrill group, 1H-indazolyl group, prynyl group, 8 of isoquinolyl group, quinolyl group, phthalazinyl group, naphthyldinyl group, quinoxalinyl group, quinazolinyl group, cinnolinyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, phenazinyl group, phenothiazine group, phenoxadinyl group and the like. ~ 14-membered fused polycyclic (preferably 2 or 3 ring) aromatic heterocyclic group.

Suitable examples of non-aromatic heterocyclic groups include:
Aziridinyl group, oxylanyl group, tiylanyl group, azetidinyl group, oxetanyl group, thietanyl group, tetrahydrothienyl group, tetrahydrofuranyl group, pyrrolinyl group, pyrrolidinyl group, imidazolinyl group, imidazolidinyl group, oxazolinyl group, oxazolidinyl group, pyrazolinyl group. Thiazolinyl group, thiazolidinyl group, tetrahydroisothiazolyl group, tetrahydrooxazolyl group, tetrahydroisooxazolyl group, piperidinyl group, piperazinyl group, tetrahydropyridinyl group, dihydropyridinyl group, dihydrothiopyranyl group, tetrahydro Pyrimidinyl group, tetrahydropyridazinyl group, dihydropyranyl group, tetrahydropyranyl group, tetrahydrothiopyranyl group, morpholinyl group, thiomorpholinyl group, azepanyl group, diazepanyl group, azepinyl group, oxepanyl group, azocanyl group, diazocanyl group, etc. 3- to 8-membered monocyclic non-aromatic heterocyclic group;
Dihydrobenzofuranyl group, dihydrobenzoimidazolyl group, dihydrobenzoxazolyl group, dihydrobenzothiazolyl group, dihydrobenzoisothiazolyl group, dihydronaphtho [2,3-b] thienyl group, tetrahydroisoquinolyl group, tetrahydro Kinoryl group, 4H-quinolinidinyl group, indolinyl group, isoindrinyl group, tetrahydrothieno [2,3-c] pyridinyl group, tetrahydrobenzoazepinyl group, tetrahydroquinoxalinyl group, tetrahydrophenanthridinyl group, hexahydro Phenothiadinyl group, hexahydrophenoxadinyl group, tetrahydrophthalazinyl group, tetrahydronaphthyldinyl group, tetrahydroquinazolinyl group, tetrahydrocinnolinyl group, tetrahydrocarbazolyl group, tetrahydro-β-carbolinyl group, tetrahydroacryl A 9-14 member condensed polycyclic (preferably 2 or 3 ring) non-aromatic heterocyclic group such as a ginyl group, a tetrahydrophenazinyl group, a tetrahydrothioxanthenyl group, an octahydroisoquinolyl group and the like.

Examples of the nitrogen-containing heterocyclic group include those containing at least one nitrogen atom as a ring-constituting atom among the above-mentioned heterocyclic groups.

Examples of the silyl group which may have a substituent include —Si (R ¹ ) (R ² ) (R ³ ) (in the formula, R ¹ to R ³ are independently hydrogen atoms and substituents, respectively. (Representing an alkyl group which may have an alkyl group or an alkoxy group which may have a substituent). Preferable examples of the silyl group which may have a substituent include a tri-C _1-6 alkylsilyl group (eg, trimethylsilyl group, tert-butyl (dimethyl) silyl group).

Examples of the syroxy group which may have ^a substituent include —OSi (R'1) ( ^R'2 ) ^{( R'3} ) (in the formula, R'1 to ^R'3 are independent of each other. Examples thereof include a hydrogen atom, an alkyl group which may have a substituent or an alkoxy group which may have a substituent). Preferable examples of the syroxy group which may have a substituent include a tri-C _1-6 alkyl syroxy group (eg, trimethyl syloxy group, tert-butyl (dimethyl) syroxy group).

Substituents that the alkyl, alkenyl and alkynyl groups can have include, for example:
(1) Cycloalkyl group (preferably C _3-8 cycloalkyl group),
(2) Aryl group (preferably C _6-14 aryl group),
(3) Alkoxy group (preferably C _1-6 alkoxy group),
(4) Cycloalkyloxy group (preferably C _3-8 cycloalkyloxy group),
(5) Aryloxy group (preferably C _6-14 aryloxy group),
(6) Aralkyloxy group (preferably _C7-16 Aralkyloxy group),
(7) Alkylthio group (preferably C _1-6 alkylthio group),
(8) Cycloalkylthio group (preferably C _3-8 cycloalkylthio group),
(9) Arylthio group (preferably _C6-14 arylthio group),
(10) Aralkylthio group (preferably _C7-16 Aralkylthio group),
(11) An amino group which may have a substituent,
(12) Heterocyclic group (preferably a 3- to 14-membered heterocyclic group),
(13) A silyl group which may have a substituent,
(14) A siroxy group which may have a substituent.

Substituents that the cycloalkyl group, cycloalkenyl group, aryl group, aralkyl group, heterocyclic group and nitrogen-containing heterocyclic group may have include, for example:
(1) Alkyl group (preferably C _1-6 alkyl group),
(2) Alkenyl group (preferably C _2-6 alkenyl group),
(3) Alkynyl group (preferably C _2-6 alkynyl group),
(4) Cycloalkyl group (preferably C _3-8 cycloalkyl group),
(5) Aryl group (preferably C _6-14 aryl group),
(6) Aralkyl group (preferably _C7-16 Aralkyl group),
(7) Alkoxy group (preferably C _1-6 alkoxy group),
(8) Cycloalkyloxy group (preferably C _3-8 cycloalkyloxy group),
(9) Aryloxy group (preferably C _6-14 aryloxy group),
(10) Aralkyloxy group (preferably _C7-16 Aralkyloxy group),
(11) Alkylthio group (preferably C _1-6 alkylthio group),
(12) Cycloalkylthio group (preferably C _3-8 cycloalkylthio group),
(13) Arylthio group (preferably _C6-14 arylthio group),
(14) Aralkylthio group (preferably _C7-16 Aralkylthio group),
(15) An amino group which may have a substituent,
(16) Heterocyclic group (preferably a 3- to 14-membered heterocyclic group),
(17) A silyl group which may have a substituent,
(18) A siroxy group which may have a substituent.

The number of carbon atoms of the divalent aliphatic hydrocarbon group is preferably 1 to 24. The divalent aliphatic hydrocarbon group may have a substituent. Examples of the divalent aliphatic hydrocarbon group include an alkandyl group, an alkenyl group, an alkenyl group, a cycloalkandyl group, a cycloalkendyl group, and a combination thereof. Examples of the combination include a combination of an alkanediyl group and a cycloalkanediyl group.

The alkanediyl group may be linear or branched. The number of carbon atoms of the alkanediyl group is preferably 1 to 24, more preferably 1 to 10, and even more preferably 1 to 6. Specific examples of the alkanediyl group include -CH ₂ -,-(CH ₂ ) ₂ -,-(CH ₂ ) ₃ -,-(CH ₂ ) ₄ -,-(CH ₂ ) ₅ -,-(CH ₂ ). ) _6- , -CH (CH ₃ )-, -C (CH ₃ ) _2- , -CH (C ₂ H ₅ )-, -CH (C ₃ H ₇ )-, -CH (CH (CH ₃ ) ₂ ) )-,-(CH (CH ₃ )) _2- , -CH ₂ -CH (CH ₃ )-, -CH (CH ₃ ) -CH _2- , -CH ₂ -CH ₂ -C (CH ₃ ) _2- , -C (CH ₃ ) ₂ -CH ₂ -CH _{2-, -CH 2 -} CH ₂ -CH ₂ -C (CH ₃ ) _2- , -C (CH ₃ ) ₂ -CH ₂ -CH ₂ -CH ₂ -Can be mentioned.

Both the alkenyl group and the alkyndiyl group may be linear or branched. The carbon atoms of the alkenyl group and the alkyndiyl group are independently, preferably 2 to 24, more preferably 2 to 10, and even more preferably 2 to 6. Specific examples of these include those in which the single bond of the specific example of the alkanediyl group having 2 or more carbon atoms is changed to a double bond or a triple bond.

The cycloalkanediyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms. Examples of the cycloalkanediyl group include a cyclopropanediyl group, a cyclobutanediyl group (eg, cyclobutane-1,3-diyl group), a cyclopentanediyl group (eg, cyclopentane-1,3-diyl group), and a cyclohexanediyl group. Examples include a group (eg, cyclohexane-1,4-diyl group), a cycloheptane diyl group (eg, cycloheptane-1,4-diyl group).

The cycloalkene diyl group has preferably 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms. Specific examples of the cycloalkenediyl group include those in which the single bond of the specific example of the cycloalkanediyl group is changed to a double bond.

Substituents that the alkandyl group, alkendyl group and alkindyl group may have include, for example:
(1) Cycloalkyl group (preferably C _3-8 cycloalkyl group),
(2) Aryl group (preferably C _6-14 aryl group),
(3) Alkoxy group (preferably C _1-6 alkoxy group),
(4) Cycloalkyloxy group (preferably C _3-8 cycloalkyloxy group),
(5) Aryloxy group (preferably C _6-14 aryloxy group),
(6) Aralkyloxy group (preferably _C7-16 Aralkyloxy group),
(7) Alkylthio group (preferably C _1-6 alkylthio group),
(8) Cycloalkylthio group (preferably C _3-8 cycloalkylthio group),
(9) Arylthio group (preferably _C6-14 arylthio group),
(10) Aralkylthio group (preferably _C7-16 Aralkylthio group),
(11) An amino group which may have a substituent,
(12) Heterocyclic group (preferably a 3- to 14-membered heterocyclic group),
(13) A silyl group which may have a substituent,
(14) A siroxy group which may have a substituent.

Substituents that the cycloalkandyl group and the cycloalkenediyl group may have include, for example:
(1) Alkyl group (preferably C _1-6 alkyl group),
(2) Alkenyl group (preferably C _2-6 alkenyl group),
(3) Alkynyl group (preferably C _2-6 alkynyl group),
(4) Cycloalkyl group (preferably C _3-8 cycloalkyl group),
(5) Aryl group (preferably C _6-14 aryl group),
(6) Aralkyl group (preferably _C7-16 Aralkyl group),
(7) Alkoxy group (preferably C _1-6 alkoxy group),
(8) Cycloalkyloxy group (preferably C _3-8 cycloalkyloxy group),
(9) Aryloxy group (preferably C _6-14 aryloxy group),
(10) Aralkyloxy group (preferably _C7-16 Aralkyloxy group),
(11) Alkylthio group (preferably C _1-6 alkylthio group),
(12) Cycloalkylthio group (preferably C _3-8 cycloalkylthio group),
(13) Arylthio group (preferably _C6-14 arylthio group),
(14) Aralkylthio group (preferably _C7-16 Aralkylthio group),
(15) An amino group which may have a substituent,
(16) Heterocyclic group (preferably a 3- to 14-membered heterocyclic group),
(17) A silyl group which may have a substituent,
(18) A siroxy group which may have a substituent.

<Method for producing organolithium compounds and their intermediates>
The present invention comprises a method for producing an organolithium compound represented by the formula (8), which comprises the following steps (a) to (d), steps (b) to (d) or steps (c) and (d). offer. In the following, the "organolithium compound represented by the formula (8)" may be abbreviated as "organolithium compound (8)" or "compound (8)". Compounds and the like represented by other formulas may be abbreviated in the same manner.

(During the ceremony,
A ¹ and A ² independently have a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, and a silyl which may have a substituent. Represents a siroxy group which may have a group or a substituent, or a nitrogen-containing heterocyclic group which may have a substituent together with a nitrogen atom to which A ¹ and A ² are bonded and adjacent to them. Form.
Z represents a divalent aliphatic hydrocarbon group which may have a substituent.
X represents a chlorine atom or a bromine atom.
HB represents an acid.
M represents an alkali metal atom.
R represents a hydrocarbon group which may have a substituent.
^Q1 represents a compound having an olefinic double bond.
Q ² represents a structural unit derived from Q ¹ .
n represents a number from 1 to 20. )

The method of the present invention including the step (c) is not a halogen-lithium exchange using metallic lithium as in the method described in Patent Document 1, but Z (that is, a divalent aliphatic hydrocarbon) of the compound (4). One of the features is that the iodine atom bonded to the group) is exchanged with the lithium atom by the organic lithium compound (5).

As described above, Z is a divalent aliphatic hydrocarbon group which may have a substituent, while Z—I in the formula (4) is a carbon atom of the divalent aliphatic hydrocarbon group. It means that the hydrocarbon atom is bonded to the iodine atom, and the state in which the substituent and the iodine atom are bonded is not included. Z-I in the formula (3) has the same meaning. Similarly, ZX in the formula (1) indicates that the carbon atom of the divalent aliphatic hydrocarbon group and X (that is, the chlorine atom or the bromine atom) are bonded to each other, and the substituent thereof. It does not include the state of being bound to X.

From the viewpoint of the reactivity of iodine-lithium exchange in the step (c) described later, it is preferable that I in the formula (4) is bonded to the primary carbon atom of the divalent aliphatic hydrocarbon group. That is, Z-I in the formula (4) preferably contains Z'- _CH2 -I (in the formula, Z'is a divalent aliphatic hydrocarbon group which may have a single bond or a substituent. Represents). Similarly, Z-I in formula (3) is preferably Z'-CH ₂ -I, and Z-X in formula (1) is preferably Z'-CH ₂ -X.
Hereinafter, steps (a) to (d) will be described in order.

<Step (a)>
In the step (a), the salt (1) and the alkali metal iodide (2) are reacted to exchange X (chlorine atom or bromine atom) contained in the salt (1) with an iodine atom to obtain the salt (3). Prepare. The alkali metal iodide (2) may be used alone or in combination of two or more.

X in the formula (1) is preferably a chlorine atom.
A ¹ and A ² in the formula (1) are independently, preferably a C _1-24 alkyl group, more preferably a C _1-6 alkyl group, and even more preferably a methyl group. The same applies to A ¹ and A ² after the formula (3).

Z in the formula (1) is preferably a divalent C _1-24 aliphatic hydrocarbon group, more preferably a C _1-24 alkanediyl group, still more preferably a C _1-6 alkanediyl group, and particularly preferably. Is-(CH ₂ ) _3- . The same applies to Z after the formula (3).

As described above, Z-X in the formula (1) is preferably Z'-CH ₂ -X (in the formula, Z'is a divalent aliphatic hydrocarbon which may have a single bond or a substituent. Represents a group). Z'is preferably a single bond or divalent C _1-23 aliphatic hydrocarbon group, more preferably a single bond or C _1-23 alkanediyl group, still more preferably a single bond or C _1-5 alkanediyl group. Yes, and particularly preferably-(CH ₂ ) _2- . The same applies to ZX and Z'after formula (3).

Preferred combinations of groups in formula (1) include the following combinations:
X is a chlorine atom or a bromine atom,
A ¹ and A ² are independently C _1-24 alkyl groups, and Z is a divalent C _1-24 aliphatic hydrocarbon group.
The preferred combinations of A ¹ , A ² and Z after the formula (3) are also as described above.
In this combination, Z-X is preferably Z'-CH ₂ -X (in the formula, Z'represents a single bond or divalent C _1-23 aliphatic hydrocarbon group).

More preferable combinations of the groups in the formula (1) include the following combinations:
X is a chlorine atom or a bromine atom,
A ¹ and A ² are independently C _1-6 alkyl groups, and Z is a C _1-24 alkanediyl group.
More preferable combinations of A ¹ , A ² and Z after the formula (3) are also as described above.
In this combination, Z-X is preferably Z'-CH ₂ -X (in the formula, Z'represents a single bond or a C _1-23 alkanediyl group).

Further preferable combinations of the groups in the formula (1) include the following combinations:
X is a chlorine atom or a bromine atom,
A ¹ and A ² are independently C _1-6 alkyl groups, and Z is a C _1-6 alkanediyl group.
More preferable combinations of A ¹ , A ² and Z after the formula (3) are also as described above.
In this combination, Z-X is preferably Z'-CH ₂ -X (in the formula, Z'represents a single bond or a C _1-5 alkanediyl group).

Particularly preferred combinations of the groups in formula (1) include the following combinations:
X is a chlorine atom,
A ¹ and A ² are methyl groups, and Z is-(CH ₂ ) _3- .
Particularly preferable combinations of A ¹ , A ² and Z after the formula (3) are also as described above.

The acid represented by HB is preferably an inorganic acid. Examples of the inorganic acid include hydrochloric acid, nitric acid, phosphoric acid, and sulfuric acid. Of these, hydrochloric acid is more preferred. That is, the salt (1) is preferably an inorganic acid salt, and more preferably a hydrochloride.

Examples of the alkali metal iodide (2) include lithium iodide, sodium iodide, potassium iodide, rubidium iodide, and cesium iodide. The alkali metal iodide (2) is preferably at least one selected from the group consisting of sodium iodide and potassium iodide, more preferably sodium iodide or potassium iodide, still more preferably sodium iodide. be.

In the step (a), the amount of the alkali metal iodide (2) used is preferably 0.1 to 20 mol, more preferably 1 to 5 mol, based on 1 mol of the salt (1).

In step (a), it is preferable to use a solvent. Examples of the solvent include water, organic solvents, ionic liquids and the like. As the solvent, only one kind may be used, or two or more kinds may be used in combination.

Examples of the organic solvent include an aliphatic hydrocarbon solvent (eg, pentane, hexane, heptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, decalin), and an aromatic hydrocarbon solvent (eg, decalin). , Benzene, toluene, xylene, mesitylen, cumene, ethylbenzene, monochlorobenzene, dichlorobenzene) and other hydrocarbon solvents; methanol, ethanol, isopropyl alcohol and other alcohol solvents; 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, tert- Ether solvents such as butylmethyl ether, dibutyl ether, cyclopentylmethyl ether; nitrile solvents such as acetonitrile and benzonitrile; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone and methyl ethyl ketone; dimethylsulfoxide; sulfolane; N, N -Dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidinone; amide solvent such as N-ethylpyrrolidinone, N-methyl-2-piperidone; 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl An imide solvent such as -3,4,5,6-tetrahydro-2 (1H) -pyrimidinone; acetic acid and the like can be mentioned.

Examples of the ionic liquid include N-butylpyridinium hexafluorophosphate, N-ethylpyridinium tetrafluoroborate, pyridiniumfluorosulfonate, 3-butyl-1-methylimidazolium tetrafluoroborate, and 3-butyl-1-methylimidazolium trifluo. Lomethanesulfonate, 3-butyl-1-methylimidazolium hexafluorophosphate, 3-butyl-1-methylimidazolium bis (trifluoromethylsulfonyl) amide, trimethylphenylammonium hexafluorophosphate, tetrabutylphosphonium tetrafluoroborate, etc. Can be mentioned.

The amount of the solvent used (when two or more kinds of solvents are used in combination, the total amount thereof) is preferably 0.1 to 20 parts by weight, more preferably 1 to 5 parts by weight with respect to 1 part by weight of the salt (1). It is a weight part.

In the step (a), a solvent, a salt (1), and an alkali metal iodide (2) are usually introduced into a reactor and reacted. The order of introduction into these reactors is not particularly limited, but it is preferable to introduce the salt (1) and the alkali metal iodide (2) and then the solvent. The salt (1) and the alkali metal iodide (2) may be introduced alone or a solution thereof may be introduced. The salt (1) and the alkali metal iodide (2) may be introduced continuously or intermittently.

In step (a), the salt (1) and the alkali metal iodide (2) are reacted in the presence of 0.5 to 5 mol of a polar solvent with respect to 1 mol of the salt (1) in a hydrocarbon solvent. Is preferable. The step (a) of this aspect may be referred to as a step (a1) below. In the step (a1), only one type of hydrocarbon solvent may be used, or two or more types may be used. The polar solvent may be only one kind or two or more kinds.

A salt is obtained by performing halogen exchange between the salt (1) and the alkali metal iodide (2) in the presence of 0.5 to 5 mol of a polar solvent with respect to 1 mol of the salt (1) in a hydrocarbon solvent. (3) can be obtained in high yield. The amount of the polar solvent used in the step (a1) is preferably 0.75 to 3.5 mol, more preferably 1 to 2 mol, with respect to 1 mol of the salt (1). When two or more kinds of polar solvents are used, the amount of the polar solvents is the total amount.

The reaction of step (a), that is, the halogen exchange between the salt (1) having a chlorine atom or a bromine atom and the alkali metal iodide (2), is the finkel that carries out the halogen exchange between chloride or bromide and NaI in acetone. Similar to the Stein reaction. This Finkelstein reaction utilizes the fact that NaI dissolves in acetone, but the NaCl or NaBr formed in this reaction precipitates without dissolving in acetone, thereby balancing the reaction of chloride or bromide with NaI. It is characterized by moving in the direction in which the desired iodide and NaCl or NaCl are formed. However, as a result of diligent studies by the present inventors, even if a hydrocarbon solvent in which the alkali metal iodide (2) is not dissolved is used, a high yield can be obtained by using the hydrocarbon solvent and the polar solvent in combination. It has been found that the salt (3) can be obtained. Therefore, the present invention also provides a method for producing an intermediate of the organic lithium compound (8) including the step (a1). Specifically, the present invention also provides a method for producing a salt (3) including the step (a1), and a method for producing a compound (4) containing the steps (a1) and (b).

The hydrocarbon solvent in the step (a1) is preferably an aliphatic hydrocarbon solvent, more preferably at least one selected from the group consisting of hexane, cyclohexane and methylcyclohexane, and further preferably a group consisting of hexane and cyclohexane. At least one selected from.

The polar solvent in the step (a1) is preferably at least one selected from the group consisting of water, alcohol solvent, amide solvent, imide solvent and ionic liquid, and more preferably from the group consisting of water, amide solvent and imide solvent. At least one of choice, more preferably water.

The amount of the hydrocarbon solvent in the step (a1) is preferably 0.5 to 10 parts by weight, more preferably 0.75 to 7.5 parts by weight, still more preferably 1 with respect to 1 part by weight of the salt (1). ~ 5 parts by weight.

The step (a) is preferably carried out using a solvent at a temperature at which the solvent is refluxed. In particular, the step (a1) is preferably performed at a temperature at which the solvent is refluxed. Further, it is preferable that the step (a) (preferably the step (a1)) is performed in an inert atmosphere such as nitrogen or argon. The reaction time is not particularly limited, but is usually 1 to 24 hours.

The solution containing the salt (3) obtained in the step (a) may be used as it is in the next step (b), or the salt (3) may be taken out from this solution by a known means. The salt (3) removed from the solution may be washed and purified by known means.

<Step (b)>
In the step (b), the salt (3) is reacted with the base to remove the acid (HB in the formula (3)) in the salt (3) to prepare the compound (4).

The base may be either an inorganic base or an organic base. The base may be only one kind or two or more kinds. Examples of the inorganic base include alkali metal hydroxides and alkaline earth metal hydroxides. Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide and the like. Examples of the hydroxide of the alkaline earth metal include calcium hydroxide and barium hydroxide. Examples of the organic base include ammonia, a primary amine, a secondary amine, a tertiary amine, and a heterocyclic amine. Examples of the primary amine include ethylamine, benzylamine, aniline and the like. Examples of the secondary amine include diethylamine, N-methyloctadecylamine, N-benzylmethylamine and the like. Examples of the tertiary amine include trimethylamine, triethylamine, tripropylamine and the like. Examples of the heterocyclic amine include pyridine and the like.

The base is preferably an inorganic base, more preferably an alkali metal hydroxide, and even more preferably sodium hydroxide. When an inorganic base (particularly sodium hydroxide) is used, it is preferable to use the aqueous solution thereof.

In the step (b), the amount of the base used is preferably 1 to 5 mol, more preferably 1 to 2 mol, relative to 1 mol of the salt (3).

In step (b), it is preferable to use a solvent. Examples of the solvent include water, organic solvents, ionic liquids and the like. As the solvent, only one kind may be used, or two or more kinds may be used in combination.

Examples of the organic solvent include an aliphatic hydrocarbon solvent (eg, pentane, hexane, heptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, decalin), and an aromatic hydrocarbon solvent (eg, decalin). , Benzene, toluene, xylene, mesitylen, cumene, ethylbenzene, monochlorobenzene, dichlorobenzene) and other hydrocarbon solvents; methanol, ethanol, isopropyl alcohol and other alcohol solvents; 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, tert- Ether solvents such as butylmethyl ether, dibutyl ether, cyclopentylmethyl ether; nitrile solvents such as acetonitrile and benzonitrile; ester solvents such as ethyl acetate and butyl acetate; ketone solvents such as acetone and methyl ethyl ketone; dimethylsulfoxide; sulfolane; N, N -Dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidinone; amide solvent such as N-ethylpyrrolidinone, N-methyl-2-piperidone; 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl An imide solvent such as -3,4,5,6-tetrahydro-2 (1H) -pyrimidinone; acetic acid and the like can be mentioned.

Examples of the ionic liquid include N-butylpyridinium hexafluorophosphate, N-ethylpyridinium tetrafluoroborate, pyridiniumfluorosulfonate, 3-butyl-1-methylimidazolium tetrafluoroborate, and 3-butyl-1-methylimidazolium trifluo. Lomethanesulfonate, 3-butyl-1-methylimidazolium hexafluorophosphate, 3-butyl-1-methylimidazolium bis (trifluoromethylsulfonyl) amide, trimethylphenylammonium hexafluorophosphate, tetrabutylphosphonium tetrafluoroborate, etc. Can be mentioned.

The amount of the solvent used (when two or more kinds of solvents are used in combination, the total amount thereof) is preferably 0.75 to 7.5 parts by weight, more preferably 1 part by weight with respect to 1 part by weight of the salt (3). ~ 7 parts by weight.

In the step (b), a solvent, a salt (3), and a base are usually introduced into a reactor and reacted. The order of introduction thereof is not particularly limited, but it is preferable to introduce the base after introducing the salt (3) and the solvent. The base may be introduced alone or a solution thereof. The introduction of the base may be carried out continuously or intermittently.

The reaction in step (b) can be carried out at a temperature equal to or higher than the melting point of the solvent used and lower than the boiling point. The reaction temperature is preferably −20 to 40 ° C. This reaction is usually carried out under normal pressure, but it can also be carried out under pressure. An inert gas such as nitrogen or argon may be used to adjust the reaction pressure. This reaction may be carried out using any of a continuous reactor, a semi-continuous reactor, and a batch reactor. The reaction time is not particularly limited, but is usually 1 to 24 hours.

When a mixture containing the salt (3) and the solvent was obtained in the step (a), the above-mentioned aqueous solution of the inorganic base (particularly sodium hydroxide) was added thereto, and the obtained mixture was stirred. It is preferable to carry out the reaction of (b). After this reaction, water derived from the organic solvent used in the step (a) and the organic phase containing the compound (4) (that is, the solution containing the compound (4)) and the aqueous solution of the inorganic base used in the step (b). It is preferable to separate from the phase. The obtained solution containing the compound (4) may be used as it is in the next step (c), or the compound (4) may be taken out from this solution by a known means. Compound (4) removed from the solution may be washed and purified by known means.

<Step (c)>
In the step (c), the compound (4) and the organolithium compound (5) are reacted to perform iodine-lithium exchange to prepare the organolithium compound (6). The organic lithium compound (5) may be only one kind or two or more kinds.

From the viewpoint of the reactivity and ease of handling of the organic lithium compound (5), R in the formula (5) is preferably a C _1-10 alkyl group or a C _6-14 aryl group, and more preferably C _1- . It is a ₆ -alkyl group, more preferably a C _1-6 alkyl group in which a lithium atom is bonded to a secondary or tertiary carbon atom, and particularly preferably a C _1-6 alkyl group in which a lithium atom is bonded to a secondary carbon atom. Is.

Specific examples of the organic lithium compound (5) include methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, and phenyllithium. Among these, sec-butyllithium and tert-butyllithium are preferable from the viewpoint of reactivity, and sec-butyllithium is more preferable from the viewpoint of reactivity and ease of handling.

In the step (c), the amount of the organolithium compound (5) used is preferably 0.5 to 5 mol, more preferably 1 to 2 mol, based on 1 mol of the compound (4).

In step (c), it is preferable to use a solvent. The solvent may be only one kind or two or more kinds. Examples of the solvent include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, and decalin; Aromatic hydrocarbon solvents such as ethylbenzene, monochlorobenzene and dichlorobenzene; ether solvents such as 1,4-dioxane, tetrahydrofuran, ethylene glycol dimethyl ether, tert-butylmethyl ether, dibutyl ether and cyclopentylmethyl ether can be mentioned. Among these, aliphatic hydrocarbons are preferable.

The amount of the solvent used (when two or more kinds of solvents are used in combination, the total amount thereof) is preferably 0.5 to 25 parts by weight, more preferably 1 to 10 parts by weight with respect to 1 part by weight of the compound (4). It is by weight, more preferably 1 to 5 parts by weight.

In the step (c), a solvent, the compound (4), and the organolithium compound (5) are usually introduced into a reactor and reacted. The order of introduction thereof is not particularly limited, but usually, the compound (4) and the solvent are introduced, and then the organolithium compound (5) is introduced. The organolithium compound (5) is preferably introduced as a solution. The introduction of the organic lithium compound (5) may be carried out continuously or intermittently.

When producing a high-quality organolithium compound (6), it is preferable to supply the compound (4) and the organolithium compound (5) into the reactor at the same time.

The supply of the compound (4) and the supply of the organolithium compound (5) into the reactor may be performed continuously or intermittently, respectively. Further, it is not necessary to coincide with the start of supply of the compound (4) and the start of supply of the organolithium compound (5), and the end of supply of the compound (4) and the end of supply of the organolithium compound (5).

The reaction temperature in the step (c) is preferably −100 ° C. to 40 ° C., more preferably −80 ° C. to 40 ° C., and even more preferably −80 ° C. to −60 ° C. The reaction is usually carried out under normal pressure, but the reaction can also be carried out under pressure. This reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon. This reaction may be carried out by any of a continuous reactor (for example, a tubular flow reactor), a semi-continuous reactor, and a batch reactor. The reaction time is not particularly limited, but is usually 1 to 24 hours.

When a mixture containing the compound (4) and the solvent was obtained in the step (b), a solution of the organolithium compound (5) was added thereto, and the obtained mixture was stirred to obtain the mixture of the step (c). It is preferable to carry out the reaction. After this reaction, the obtained solution containing the organolithium compound (6) may be used as it is in the next step (d), and after taking out the organolithium compound (6) from this solution by a known means, Cleaning and purification may be performed by known means. For example, the solution containing the organolithium compound (6) is cooled, the precipitate containing the organolithium compound (6) is collected by filtration, dissolved in a hydrocarbon solvent, and then the insoluble component is removed from the obtained solution by filtration. You may. It is preferable to use the solution containing the organolithium compound (6) in the next step (d).

<Step (d)>
In the step (d), the organolithium compound (6) is reacted with the compound (7) having an olefinic double bond to prepare the organolithium compound (8). This reaction proceeds by the same mechanism as anionic polymerization of a monomer having an olefinic double bond using an organolithium compound as a polymerization initiator. More specifically, ^Q1 of the formula (7), which is a compound having an olefinic double bond, is inserted between -Z ^- Li ⁺ in the organolithium compound (6), and -Z- (Q). ² ) ^{-Li +} is formed. By repeating such a reaction, —Z— ( ^Q2 ) _n —Li in the formula (8) is formed.

The compound (7) having an olefinic double bond may be only one kind or two or more kinds. Compound (7) is preferably a diene compound. Examples of the diene compound include 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene, 1,3-hexadiene, 1,4-pentadiene, and 1,5-hexadiene. And so on. The compound (7) is more preferably a conjugated diene compound, more preferably from 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and 1,3-hexadiene. At least one selected from the group consisting of 1,3-butadiene and isoprene, particularly preferably at least one selected from the group consisting of 1,3-butadiene and isoprene, and most preferably isoprene.

In the step (d), the amount of the compound (7) used is preferably 1 to 20 mol, more preferably 2 to 5 mol, based on 1 mol of the organolithium compound (6). That is, n in the formula (8) is preferably 1 to 20, more preferably 2 to 5. In addition, this n represents the number of ^Q2 (that is, the structural unit derived from ^Q1 which is a compound having an olefinic double bond) per molecule of an organic lithium compound (8).

In step (d), it is preferable to use a solvent. The solvent may be only one kind or two or more kinds. Examples of the solvent include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, and decalin; benzene, toluene, xylene, mesitylene, cumene, and the like. Examples thereof include aromatic hydrocarbon solvents such as ethylbenzene, monochlorobenzene and dichlorobenzene. Among these, aliphatic hydrocarbons are preferable.

The amount of the solvent used (when two or more kinds of solvents are used in combination, the total amount thereof) is preferably 1 to 50 parts by weight, more preferably 1 to 30 parts by weight with respect to 1 part by weight of the organolithium compound (6). It is a weight part.

In the step (d), the reaction can be smoothly proceeded by using the additive. The additive may be only one kind or two or more kinds. Examples of the additive include dimethoxybenzene, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, 2,2-di (tetrahydrofuryl) propane, 2- (2-ethoxyethoxy) -2-. Examples thereof include methylpropane, triethylamine, pyridine, N-methylmorpholine and tetramethylethylenediamine. Among these, tetrahydrofuran, ethylene glycol dimethylate and tetramethylethylenediamine are preferable, tetrahydrofuran and ethylene glycol dimethylate are more preferable, and tetrahydrofuran is further preferable. As the solid additive (for example, a powdery additive), a molded one may be used, one supported on a carrier may be used, or one immobilized on a polymer compound is used. You may.

When an additive is used, the amount thereof is preferably 0.1 to 10 mol, more preferably 0.5 to 7.5 mol, based on 1 mol of the organolithium compound (6).

In the step (d), a solvent, an organolithium compound (6), a compound (7), and if necessary, an additive are usually introduced into the reactor and reacted. The order of introduction thereof is not particularly limited, but it is preferable to introduce the organic lithium compound (6) and the solvent, and then the compound (7).

When the additive is used in the step (d), it is preferable to introduce the organolithium compound (6) and the solvent, then the additive, and then the compound (7). The entire amount of the additive may be introduced into the reactor together with the organolithium compound (6) and the solvent, or a part thereof may be introduced into the reactor in advance, and then the balance may be introduced into the organolithium compound (6) and the rest. It may be introduced into the reactor together with the solvent. It is preferable to introduce the entire amount of the compound (7) into the reactor into which the organolithium compound (6), the solvent and the additive have been introduced. Compound (7) may be introduced alone or a solution thereof. The introduction of compound (7) may be carried out continuously or intermittently.

The reaction temperature in the step (d) is preferably 10 to 80 ° C, more preferably 10 to 60 ° C. The reaction is usually carried out under normal pressure, but the reaction can also be carried out under pressure. An inert gas such as nitrogen or argon may be used to adjust the reaction pressure. Further, this reaction is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon. This reaction may be carried out using any of a continuous reactor, a semi-continuous reactor, and a batch reactor. The reaction time is not particularly limited, but is usually 30 minutes to 24 hours.

The solution containing the organolithium compound (8) obtained in the step (d) may be used as it is, for example, for the polymerization of a conjugated diene compound as described later, and the organolithium compound (from this solution by a known means). After taking out 8), washing and purification may be carried out by known means. It is preferred that the solution containing the organolithium compound (8) be used, for example, for the polymerization of the conjugated diene compound. The concentration of the organolithium compound (8) in the solution is preferably 0.01 to 10 mol / L, more preferably 0.1 to 1 mol / L.

<Polymerization of conjugated diene compound>
The present invention also comprises a step of producing the organolithium compound (8) as described above and a step of polymerizing the conjugated diene compound in the presence of the organolithium compound (8) to produce a conjugated diene-based polymer. offer. This polymerization is an anionic polymerization using the organolithium compound (8) as a polymerization initiator, and those skilled in the art can appropriately set the conditions.

The conjugated diene compound may be only one kind or two or more kinds. The conjugated diene compound is preferably at least one selected from the group consisting of 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethyl-1,3-butadiene and 1,3-hexadiene. It is more preferably at least one selected from the group consisting of 1,3-butadiene and isoprene, and even more preferably 1,3-butadiene. The amount of the conjugated diene compound used is preferably 10 to 50,000 mol, more preferably 150 to 30,000 mol, relative to 1 mol of the organolithium compound (8).

In the polymerization of the conjugated diene compound, another monomer different from the conjugated diene compound may be used. The other monomer may be only one kind or two or more kinds. Examples of other monomers include aromatic vinyl compounds. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, divinylbenzene, trivinylbenzene, and divinylnaphthalene. The other monomer is preferably at least one selected from the group consisting of styrene, α-methylstyrene, vinyltoluene, vinylnaphthalene, divinylbenzene, trivinylbenzene and divinylnaphthalene, and more preferably styrene. When other monomers are used, the amount thereof is preferably 0.5 to 50 mol, more preferably 5 to 40 mol, relative to 100 mol of the conjugated diene compound.

In the polymerization of the conjugated diene compound, a reagent may be added to the reaction mixture of the polymerization in order to improve the characteristics of the obtained polymer or the characteristics of the product obtained from the polymer (for example, the fuel efficiency of the tire). Only one kind of reagent may be used, or two or more kinds of reagents may be used.

Examples of the reagent include bis (dimethylamino) methylvinylsilane, bis (ethylmethylamino) methylvinylsilane, bis (diethylamino) methylvinylsilane, bis (ethyl-n-propylamino) methylvinylsilane, and bis (ethylisopropylamino) methylvinylsilane. , Bis (di (n-propyl) amino) methylvinylsilane, bis (diisopropylamino) methylvinylsilane, bis (n-butyl-n-propylamino) methylvinylsilane, bis (di (n-butyl) amino) methylvinylsilane, bis (Dimethylamino) ethylvinylsilane, bis (ethylmethylamino) ethylvinylsilane, bis (diethylamino) ethylvinylsilane, bis (ethyl-n-propylamino) ethylvinylsilane, bis (ethylisopropylamino) ethylvinylsilane, bis (di (n-) Propyl) amino) ethylvinylsilane, bis (diisopropylamino) ethylvinylsilane, bis (n-butyl-n-propylamino) ethylvinylsilane, bis (di (n-butyl) amino) ethylvinylsilane, bis (dimethylamino) propylvinylsilane, Bis (ethylmethylamino) propylvinylsilane, bis (diethylamino) propylvinylsilane, bis (ethyl-n-propylamino) propylvinylsilane, bis (ethylisopropylamino) propylvinylsilane, bis (di (n-propyl) amino) propylvinylsilane, Bis (diisopropylamino) propylvinylsilane, bis (n-butyl-n-propylamino) propylvinylsilane, bis (di (n-butyl) amino) propylvinylsilane, bis (dimethylamino) butylvinylsilane, bis (ethylmethylamino) butyl Vinyl silane, bis (diethylamino) butyl vinyl silane, bis (ethyl-n-propylamino) butyl vinyl silane, bis (ethyl isopropyl amino) butyl vinyl silane, bis (di (n-propyl) amino) butyl vinyl silane, bis (diisopropyl amino) butyl vinyl silane , Bis (n-butyl-n-propylamino) butylvinylsilane, bis (di (n-butyl) amino) butylvinylsilane, N- (2-dimethylaminoethyl) acrylamide, N- (2-diethylaminoethyl) acrylamide, N -(3-Dimethylaminopropyl) acrylamide, N- (3-diethylaminopropyl) ac Lilamide, N- (4-dimethylaminobutyl) acrylamide, N- (4-diethylaminobutyl) acrylamide, N- (3-di (glycidyl) aminopropyl) acrylamide, N- (3-di (tetrahydrofurfuryl) aminopropyl) ) Acrylamide, N- (3-morpholinopropyl) acrylamide, N- (2-dimethylaminoethyl) methacrylicamide, N- (2-diethylaminoethyl) methacrylicamide, N- (3-dimethylaminopropyl) methacrylicamide, N- (3-diethylaminopropyl) methacrylicamide, N- (4-dimethylaminobutyl) methacrylicamide, N- (4-diethylaminobutyl) methacrylicamide, N- (3-di (glycidyl) aminopropyl) methacrylicamide, [3- (Dimethylamino) propyl] trimethoxysilane, [3- (diethylamino) propyl] trimethoxysilane, [3- (ethylmethylamino) propyl] trimethoxysilane, [3- (dimethylamino) propyl] triethoxysilane, [ [3- (Dialkylamino) propyl] trialkoxysilane, 3- (dimethylamino) propyl] methyldimethoxysilane, such as 3- (diethylamino) propyl] triethoxysilane, [3- (ethylmethylamino) propyl] triethoxysilane , [3- (diethylamino) propyl] methyldimethoxysilane, [3- (ethylmethylamino) propyl] methyldimethoxysilane, [3- (dimethylamino) propyl] ethyldimethoxysilane, [3- (diethylamino) propyl] ethyldimethoxy Silane, [3- (ethylmethylamino) propyl] ethyldimethoxysilane, [3- (dimethylamino) propyl] methyldiethoxysilane, [3- (diethylamino) propyl] methyldiethoxysilane, [3- (ethylmethylamino) propyl] ) Propyl] methyldiethoxysilane, [3- (dimethylamino) propyl] ethyldiethoxysilane, [3- (diethylamino) propyl] ethyldiethoxysilane, [3- (ethylmethylamino) propyl] ethyldiethoxysilane, etc. [3- (Dialkylamino) propyl] alkyldialkoxysilane.

When reagents are used, the amount thereof (in the case of using two or more kinds of reagents, the total amount thereof) is preferably 0.01 to 0.25 mol, more preferably 0.01 to 0.25 mol, based on 100 mol of the conjugated diene compound. It is 0.05 to 0.15 mol.

In the polymerization, it is preferable to use a solvent. The solvent may be only one kind or two or more kinds. Examples of the solvent include aliphatic hydrocarbon solvents such as pentane, hexane, heptane, octane, isooctane, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, cyclooctane, and decalin; benzene, toluene, xylene, mesitylene, cumene, and the like. Examples thereof include aromatic hydrocarbon solvents such as ethylbenzene, monochlorobenzene and dichlorobenzene. Among these, aliphatic hydrocarbons are preferable.

The amount of the solvent used (when two or more kinds of solvents are used in combination, the total amount thereof) is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, based on 1 part by weight of the conjugated diene compound. be.

By using the additive, the polymerization can proceed smoothly. The additive may be only one kind or two or more kinds. Examples of the additive include dimethoxybenzene, tetrahydrofuran, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, 2,2-di (tetrahydrofuryl) propane, 2- (2-ethoxyethoxy) -2-. Examples thereof include methylpropane, triethylamine, pyridine, N-methylmorpholine and tetramethylethylenediamine. Among these, tetrahydrofuran, ethylene glycol diethyl ether, diethylene glycol dibutyl ether, and tetramethylethylene diamine are preferable, tetrahydrofuran and ethylene glycol diethyl ether are more preferable, and tetrahydrofuran is further preferable. When an additive is used, the amount thereof is preferably 0.01 to 100 mol, more preferably 0.1 to 10 mol, based on 1 mol of the organolithium compound (8).

The polymerization is preferably carried out in an atmosphere of an inert gas such as nitrogen or argon. The polymerization temperature is preferably 25 to 100 ° C, more preferably 35 to 90 ° C. The polymerization time is not particularly limited, but is usually 30 minutes to 24 hours.

It is preferable to add a deactivating agent to the solution containing the obtained polymer to stop the polymerization. The deactivating agent may be only one kind or two or more kinds. Examples of the deactivating agent include alcohols such as methanol, isopropyl alcohol, 1-butanol, and water. When a deactivating agent is used, the amount thereof is preferably 1 to 100 mol, more preferably 1.1 to 10 mol, based on 1 mol of the organolithium compound (8).

The polymer can be taken out from the solution containing the obtained polymer by removing the solvent and the like by a known method (for example, drying under reduced pressure).

Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to the following examples. In Examples and Comparative Examples, the content, yield and conversion rate of each compound were calculated by proton nuclear magnetic resonance ( ¹ H NMR) spectral analysis and weight measurement. In addition, the physical properties of the copolymer and the vulcanized sheet obtained in the examples described later were evaluated by the following method.

1. 1. Mooney viscosity of copolymer (ML1 + 4)
The Mooney viscosity of the copolymer was measured at 100 ° C. according to JIS K6300 (1994).

2. 2. Vinyl Bonding Amount of Copolymer The vinyl binding amount (mol%) of the copolymer was determined from the absorption intensity near the absorption peak of the vinyl group, 910 cm ^-1 , by infrared spectroscopy.

3. 3. Content of styrene unit of copolymer According to JIS K6383 (1995), the content (% by weight) of styrene unit of the copolymer was determined from the refractive index.

4. Vulcanized sheet tan δ (70 ° C) and tan δ (0 ° C)
A strip-shaped test piece having a width of 1 mm and a length of 40 mm was punched out from the vulcanization sheet and used for the test. The measurement was performed by a viscoelasticity measuring device (manufactured by Ueshima Seisakusho Co., Ltd.) under the conditions of 1% strain and 10 Hz frequency, loss tangent (tan δ (70 ° C)) of the test piece at a temperature of 70 ° C, and a test at a temperature of 0 ° C. The loss tangent (tan δ (0 ° C.)) of the piece was measured. The smaller the tan δ (70 ° C), the better the fuel efficiency, and the larger the tan δ (0 ° C), the better the grip.

Example 1: Steps (a) and (b)
In a reactor equipped with a reflux cooler, thermocouple and stirrer, 161.3 g (1 mol) of 3-chloro-N, N-dimethylpropylamine hydrochloride, 302.8 g (2 mol) of sodium iodide, 18 g of water ( 1 mol) and cyclohexane (5 parts by weight with respect to 1 part by weight of 3-chloro-N, N-dimethylpropylamine hydrochloride) were added, and nitrogen was introduced into the reactor to create a nitrogen atmosphere inside. .. The temperature in the reactor was then raised to 80 ° C. while stirring the mixture, and the mixture was refluxed at the same temperature with stirring for 3 hours.

Then, while stirring the mixture, the temperature inside the reactor is cooled to 0 to 10 ° C., and 806 mL (1 mol of sodium hydroxide) of 1.24 M aqueous sodium hydroxide solution is added to eliminate the precipitation component in the mixture. After stirring the mixture until (about 0.5 hours), the aqueous phase and the organic phase were separated to obtain 980.2 g of a cyclohexane solution of 3-iodo-N, N-dimethylpropylamine as the organic phase. The content of 3-iodo-N, N-dimethylpropylamine in the solution was 20.6% by weight, and the yield was 95.0%.

Example 2: Steps (a) and (b)
In a reactor equipped with a reflux cooler, a thermocouple and a stirrer, 161.3 g (1 mol) of 3-chloro-N, N-dimethylpropylamine hydrochloride, 302.8 g (2 mol) of sodium iodide, 36 g of water ( 2 mol) and cyclohexane (5 parts by weight with respect to 1 part by weight of 3-chloro-N, N-dimethylpropylamine hydrochloride) were added, and nitrogen was introduced into the reactor to create a nitrogen atmosphere inside. .. The temperature in the reactor was then raised to 80 ° C. while stirring the mixture, and the mixture was refluxed at the same temperature with stirring for 3 hours.

Then, while stirring the mixture, the temperature inside the reactor is cooled to 0 to 10 ° C., and 806 mL (1 mol of sodium hydroxide) of 1.24 M aqueous sodium hydroxide solution is added to eliminate the precipitation component in the mixture. After stirring the mixture until (about 0.5 hours), the aqueous phase and the organic phase were separated to obtain 983.3 g of a cyclohexane solution of 3-iodo-N, N-dimethylpropylamine as the organic phase. The content of 3-iodo-N, N-dimethylpropylamine in the solution was 21.3% by weight, and the yield was 99.8%.

Example 3: Steps (a) and (b)
In a reactor equipped with a reflux cooler, a thermocouple and a stirrer, 161.3 g (1 mol) of 3-chloro-N, N-dimethylpropylamine hydrochloride, 302.8 g (2 mol) of sodium iodide, 90 g of water ( 5 mol) and cyclohexane (5 parts by weight with respect to 1 part by weight of 3-chloro-N, N-dimethylpropylamine hydrochloride) were added, and nitrogen was introduced into the reactor to create a nitrogen atmosphere inside. .. The temperature in the reactor was then raised to 80 ° C. while stirring the mixture, and the mixture was refluxed at the same temperature with stirring for 3 hours.

Then, while stirring the mixture, the temperature inside the reactor is cooled to 0 to 10 ° C., and 806 mL (1 mol of sodium hydroxide) of 1.24 M aqueous sodium hydroxide solution is added to eliminate the precipitation component in the mixture. After stirring the mixture until (about 0.5 hours), the aqueous phase and the organic phase were separated to obtain 972.6 g of a cyclohexane solution of 3-iodo-N, N-dimethylpropylamine as the organic phase. The content of 3-iodo-N, N-dimethylpropylamine in the solution was 18.0% by weight, and the yield was 82.0%.

Example 4: Steps (a) and (b)
161.3 g (1 mol) of 3-chloro-N, N-dimethylpropylamine hydrochloride, 302.8 g (2 mol) of sodium iodide, 1,3 in a reactor equipped with a reflux cooler, a thermocouple and a stirrer. -Dimethyl-2-imidazolidinone 114.0 g (1 mol) and hexane (5 parts by weight with respect to 1 part by weight of 3-chloro-N, N-dimethylpropylamine hydrochloride) were added, and nitrogen was added to the reactor. Was introduced, and the inside was made under a nitrogen atmosphere. The temperature in the reactor was then raised to 80 ° C. while stirring the mixture, and the mixture was refluxed at the same temperature with stirring for 5 hours.

Then, while stirring the mixture, the temperature inside the reactor is cooled to 0 to 10 ° C., and 806 mL (1 mol of sodium hydroxide) of 1.24 M aqueous sodium hydroxide solution is added to eliminate the precipitation component in the mixture. After stirring the mixture until (about 0.5 hours), the aqueous phase and the organic phase were separated to obtain 863.3 g of a hexane solution of 3-iodo-N, N-dimethylpropylamine as the organic phase. The content of 3-iodo-N, N-dimethylpropylamine in the solution was 22.5% by weight, and the yield was 91.0%.

Example 5: Steps (a) and (b)
In a reactor equipped with a reflux cooler, a thermocouple and a stirrer, 161.3 g (1 mol) of 3-chloro-N, N-dimethylpropylamine hydrochloride, 302.8 g (2 mol) of sodium iodide, 36 g of water ( 2 mol) and hexane (5 parts by weight with respect to 1 part by weight of 3-chloro-N, N-dimethylpropylamine hydrochloride) were added, nitrogen was introduced into the reactor, and the inside was subjected to a nitrogen atmosphere. did. The temperature in the reactor was then raised to 80 ° C. while stirring the mixture, and the mixture was refluxed at the same temperature with stirring for 5 hours.

Then, while stirring the mixture, the temperature inside the reactor is cooled to 0 to 10 ° C., and 806 mL (1 mol of sodium hydroxide) of 1.24 M aqueous sodium hydroxide solution is added to eliminate the precipitation component in the mixture. After stirring the mixture until (about 0.5 hours), the aqueous phase and the organic phase were separated to obtain 882.3 g of a hexane solution of 3-iodo-N, N-dimethylpropylamine as the organic phase. The content of 3-iodo-N, N-dimethylpropylamine in the solution was 22.5% by weight, and the yield was 93.0%.

Example 6: Steps (c) and (d)
882.3 g (22.5 wt%, 0.93 mol) of a hexane solution of 3-iodo-N, N-dimethylpropylamine obtained in the same manner as in Example 5 in a reactor equipped with a thermocouple and a stirrer. Was added, nitrogen was introduced into the reactor, and the inside thereof was brought into a nitrogen atmosphere. Next, the temperature inside the reactor was cooled to −78 ° C. while stirring the hexane solution, and then the cyclohexane solution of sec-butyllithium (1. 0M, 0.93 mol) was added dropwise over 5 hours to carry out the reaction.

Then, after filtering the reaction mixture at −20 ° C. under a nitrogen atmosphere, the obtained residue (that is, the mixture containing the organic lithium compound (6) which is the target product of the step (c)) is subjected to cyclohexane (that is, a mixture containing the organic lithium compound (6) which is the target of the step (c)) at 45 ° C. Organic lithium compound (6) Mixing and stirring with 1 part by weight of cyclohexane (35 parts by weight), the insoluble component of the obtained mixture is removed by filtration, and the obtained filtrate is used as a reflux cooler, a thermocouple and a thermocouple. It was transferred to a reactor equipped with a stirrer. Next, while stirring the filtrate, the temperature inside the reactor was raised to 45 ° C. under a nitrogen atmosphere, and then 129.4 g (1.9 mol) of isoprene was added dropwise to raise the temperature inside the reactor to 65 ° C. After stirring the mixture for 1 hour, 2780 g of a solution of the organolithium compound (that is, compound (8)) to which isoprene was added was obtained. The content of the organolithium compound to which isoprene was added in the solution was 5.9% by mass, and the isoprene conversion rate was 100%.

Example 7: Steps (c) and (d)
After adding 882.3 g (22.5% by weight, 0.93 mol) of the hexane solution of 3-iodo-N, N-dimethylpropylamine obtained in Example 5 to the reactor equipped with a thermocouple and a stirrer. , Nitrogen was introduced into the reactor, and the inside was made into a nitrogen atmosphere. Next, the temperature inside the reactor was cooled to −78 ° C. while stirring the hexane solution, and then the cyclohexane solution of sec-butyllithium (1. 0M, 0.93 mol) was added dropwise over 5 hours to carry out the reaction.

Then, after filtering the reaction mixture at −20 ° C. under a nitrogen atmosphere, the obtained residue (that is, the mixture containing the organic lithium compound (6) which is the target product of the step (c)) is mixed with tetrahydrofuran at 25 ° C. Mixed solvent of cyclohexane (concentration of tetrahydrofuran in mixed solvent: 20% by weight, amount of cyclohexane per 1 part by weight of organic lithium compound (6): 17 parts by weight, amount of tetrahydrofuran per mol of organic lithium compound (6): 5 mol) The insoluble component of the obtained mixture was removed by filtration, and the obtained filtrate was transferred to a reactor equipped with a reflux cooler, a thermocouple and a stirrer. Next, while stirring the filtrate, the temperature inside the reactor was raised to 25 ° C. under a nitrogen atmosphere, and then 129.4 g (1.9 mol) of isoprene was added dropwise to raise the temperature inside the reactor to 25 ° C. After stirring the mixture for 30 minutes, 2040 g of a solution of the organolithium compound (that is, compound (8)) to which isoprene was added was obtained. The content of the organolithium compound to which isoprene was added in the solution was 10.5% by mass, and the isoprene conversion rate was 100%.

From the results of ¹ H NMR spectrum analysis, the number of isoprene added per molecule of the organolithium compound added with isoprene (that is, n in the formula (8)) was 2.2.

The amount of the residue of the organolithium compound (8) obtained in Example 7 was measured as follows. Specifically, in the gas chromatograph obtained by analyzing the organolithium compound (8) by gas chromatography under the following equipment and conditions, all the peaks excluding the peak areas of cyclohexane, tetrahydrofuran and the analytical reagent (chlorotrimethylsilane). Ratio (area%) of the peak area of the residue without carbon-lithium bond to the area (that is, the sum of the peak area of the organolithium compound (8) and the peak area of the residue without carbon-lithium bond). Was calculated. As this analysis sample, a solution obtained by reacting 1 mol of the organolithium compound (8) with 1.2 mol of chlorotrimethylsilane was used.
-Gas chromatography (1) Equipment: Agilent Technologies 7890A GC / 5975C MSD system (2) Separation column: Agilent J & W DB5MS, length 30 m, inner diameter 0.25 mm, membrane pressure 0.25 μm
(3) Column temperature program: 40 ° C (holding for 2 minutes) -heating rate 10 ° C / min-300 ° C (holding for 30 minutes)
(4) Carrier gas: helium 1.0 mL / min (constant flow mode)
(5) Vaporization chamber temperature: 300 ° C
(6) Injection mode: split, split ratio 100: 1
(7) Injection amount: 1 μL
-Gas chromatograph mass spectrometry (8) Interface temperature: 300 ° C
(9) Measurement mode: Scan (m / z 11 to m / z 700)

The ratio of the peak area of the residue having no carbon-lithium bond in the gas chromatograph of the organolithium compound (8) obtained in Example 7 measured as described above is the peak of the organolithium compound (8). It was 5.1 area% with respect to the total of the area and the peak area of the residue.

Example 8: Polymerization of Conjugate Diene Compound and Production of Sulfurized Sheet The inside of a stainless steel polymerization reactor having an internal volume of 20 L is washed, dried, replaced with dry nitrogen, and industrial hexane (density 680 kg / m ³ ) is contained therein. ) 10.2 kg, 1,3-butadiene 608 g, styrene 192 g, tetrahydrofuran 6.1 mL, ethylene glycol diethyl ether 4.36 mL were added. Next, 85.5 mL of the solution containing 14.29 mmol of the organolithium compound obtained in Example 7 was rapidly added at 30 ° C., and polymerization was started at that temperature.

The stirring speed was 130 rpm, the temperature inside the polymerization reactor was 65 ° C., and 1,3-butadiene was continuously supplied into the polymerization reaction vessel at 365 g / hour for 2.5 hours and styrene at 144 g / hour for 2 hours. Then, the polymerization was carried out for a total of 3 hours. The total supply of 1,3-butadiene was 912 g and the total supply of styrene was 288 g. On the way, 25 minutes after the start of the polymerization, 20 mL of a hexane solution containing 1.83 g of bis (diethylamino) methylvinylsilane was rapidly poured into the polymerization reactor.

Next, the obtained polymerization reaction solution was stirred at a stirring speed of 130 rpm, 14.29 mmol of N- (3-dimethylaminopropyl) acrylamide was added at 65 ° C., and the mixture was stirred at that temperature for 15 minutes. To the polymerization reaction solution, 20 mL of a hexane solution containing 0.87 mL of methanol was added at 65 ° C., and the polymerization reaction solution was further stirred at that temperature for 30 minutes.

Next, in the obtained polymerization reaction solution, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenylacrylate (manufactured by Sumitomo Chemical Co., Ltd.) was added as an antioxidant. , Product name: Sumilyzer GM) 8.0 g, and Pentaerythrityltetrakis (3-laurylthiopropionate) (manufactured by Sumitomo Chemical Co., Ltd., Product name: Sumilyzer TP-D) 4.0 g, and then the polymer. The solution was allowed to stand at room temperature for 24 hours to evaporate the solvent and further dried under reduced pressure at 55 ° C. for 12 hours to obtain a styrene-1,3-butadiene copolymer (that is, styrene-butadiene rubber). Table 1 shows the evaluation results of the Mooney viscosity, vinyl bond amount and styrene unit content of the copolymer measured as described above.

100 parts by weight of the obtained copolymer, 78.4 parts by weight of silica (manufactured by Degussa, trade name: Ultrasil VN3-G), 6.4 parts by weight of a silane coupling agent (manufactured by Degussa, trade name: Si69). , Carbon black (manufactured by Mitsubishi Chemical Co., Ltd., product name: Diamond Black N339) 6.4 parts by weight, extension oil (manufactured by Japan Energy Co., Ltd., product name: JOMO Process NC-140) 47.6 parts by weight, anti-aging agent (Sumitomo) Chemical Co., Ltd., trade name: Antigen 3C) 1.5 parts by weight, stearate 2 parts by weight, zinc flower 2 parts by weight, vulture accelerator (Sumitomo Chemical Co., Ltd., trade name: Soxinol CZ) 1 part by weight, vulture Accelerator (manufactured by Sumitomo Chemical Co., Ltd., product name: Soxinol D) 1 part by weight, wax (manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., product name: Sannock N) 1.5 parts by weight, sulfur 1.4 parts by weight, processing aid (Manufactured by Schill & Seilacher, trade name: Stractol EF 44) was kneaded by 1 part by weight with a laboplast mill to prepare a composition of a copolymer. The composition of the obtained copolymer was formed into a sheet with a 6-inch roll, and the sheet was heated at 160 ° C. for 55 minutes to vulcanize to prepare a vulcanized sheet. Table 1 shows the evaluation results of the vulcanization sheet measured as described above.

Comparative Example 1: Polymerization of Conjugate Diene Compound and Production of Sulfurized Sheet Commercially available organic lithium compound (8) solution (FMC "AI-200CE2 (cyclohexane solution)", A ¹ and A ² in formula (8) are methyl Example 8 using a solution containing an organic lithium compound (8) in which Z is − (CH ₂ ) ₃ −, Q ² is a structural unit derived from isoprene, and n is 2. In the same manner as above, the polymerization of the conjugated diene compound and the production of the vulture sheet were carried out. However, the amount of the organolithium compound (8) used in the polymerization was set to 15.50 mmol. Further, the ratio of the peak area of the residue having no carbon-lithium bond in the gas chromatograph of the commercially available organolithium compound (8) measured in the same manner as in Example 7 is the peak area of the organolithium compound (8). It was 9.1 area% with respect to the total of the area and the peak area of the residue. Table 1 shows the evaluation results of the vulcanization sheet.

The vulcanized product (vulcanized sheet) obtained in Example 8 is excellent in fuel efficiency and grip. Therefore, this vulcanized product is suitably used for tire manufacturing.

According to the present invention, it is possible to produce an organolithium compound having an amino group under industrially advantageous conditions without using metallic lithium. The organolithium compound having an amino group thus obtained is useful as, for example, a polymerization initiator.

Claims (8)

Step (a), a step (a) of reacting a salt represented by the formula (1) with an alkali metal iodide represented by the formula (2) to obtain a salt represented by the formula (3).
Step (b), a step (b) of reacting a salt represented by the formula (3) with a base to obtain a compound represented by the formula (4).
The step (c) and the formula (6) of reacting the compound represented by the formula (4) with the organolithium compound represented by the formula (5) to obtain the organolithium compound represented by the formula (6). Represented by the formula (8), which comprises the step (d) of reacting the organolithium compound represented by the formula (7) with the diene compound represented by the formula (7) to obtain the organolithium compound represented by the formula (8). A method for producing an organolithium compound.

(During the ceremony,
A ¹ and A ² independently have a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, and a silyl which may have a substituent. Represents a siroxy group which may have a group or a substituent, or a nitrogen-containing heterocyclic group which may have a substituent together with a nitrogen atom to which A ¹ and A ² are bonded and adjacent to them. Form.
Z represents a divalent aliphatic hydrocarbon group which may have a substituent.
X represents a chlorine atom or a bromine atom.
HB represents an acid.
M represents an alkali metal atom.
R represents a hydrocarbon group which may have a substituent.
^Q1 represents a diene compound.
Q ² represents a structural unit derived from Q ¹ .
n represents 1 to 20. ) In the step (a), the salt represented by the formula (1) and the formula in the presence of 0.5 to 5 mol of the polar solvent with respect to 1 mol of the salt represented by the formula (1) in the hydrocarbon solvent. The method according to claim 1, wherein the alkali metal iodide represented by (2) is reacted. Step (b), a step (b) of reacting a salt represented by the formula (3) with a base to obtain a compound represented by the formula (4).
The step (c) and the formula (6) of reacting the compound represented by the formula (4) with the organolithium compound represented by the formula (5) to obtain the organolithium compound represented by the formula (6). Represented by the formula (8), which comprises the step (d) of reacting the organolithium compound represented by the formula (7) with the diene compound represented by the formula (7) to obtain the organolithium compound represented by the formula (8). A method for producing an organolithium compound.

(During the ceremony,
A ¹ and A ² independently have a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, and a silyl which may have a substituent. Represents a siroxy group which may have a group or a substituent, or a nitrogen-containing heterocyclic group which may have a substituent together with a nitrogen atom to which A ¹ and A ² are bonded and adjacent to them. Form.
Z represents a divalent aliphatic hydrocarbon group which may have a substituent.
HB represents an acid.
R represents a hydrocarbon group which may have a substituent.
^Q1 represents a diene compound.
Q ² represents a structural unit derived from Q ¹ .
n represents 1 to 20. ) The step (c) and the formula (6) of reacting the compound represented by the formula (4) with the organolithium compound represented by the formula (5) to obtain the organolithium compound represented by the formula (6). Step (d) of reacting the organolithium compound represented by the formula (7) with the diene compound represented by the formula (7) to obtain the organolithium compound represented by the formula (8):
A method for producing an organic lithium compound represented by the formula (8).

(During the ceremony,
A ¹ and A ² independently have a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, and a silyl which may have a substituent. Represents a siroxy group which may have a group or a substituent, or a nitrogen-containing heterocyclic group which may have a substituent together with a nitrogen atom to which A ¹ and A ² are bonded and adjacent to them. Form.
Z represents a divalent aliphatic hydrocarbon group which may have a substituent.
R represents a hydrocarbon group which may have a substituent.
^Q1 represents a diene compound.
Q ² represents a structural unit derived from Q ¹ .
n represents 1 to 20. ) The step of producing the organolithium compound represented by the formula (8) by the method according to any one of claims 1 to 4 , and the conjugated diene in the presence of the organolithium compound represented by the formula (8). A method for producing a conjugated diene-based polymer, which comprises a step of polymerizing a compound. In the hydrocarbon solvent, the salt represented by the formula (1) and the salt represented by the formula (2) are represented in the presence of 0.5 to 5 mol of the polar solvent with respect to 1 mol of the salt represented by the formula (1). In the step (a) of reacting with an alkali metal iodide to obtain a salt represented by the formula (3), and reacting the salt represented by the formula (3) with a base, the formula (4) is used. Step (b) to obtain the represented compound
A method for producing a compound represented by the formula (4), which comprises.

(During the ceremony,
A ¹ and A ² independently have a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, and a silyl which may have a substituent. Represents a siroxy group which may have a group or a substituent, or a nitrogen-containing heterocyclic group which may have a substituent together with a nitrogen atom to which A ¹ and A ² are bonded and adjacent to them. Form.
Z represents a divalent aliphatic hydrocarbon group which may have a substituent.
X represents a chlorine atom or a bromine atom.
HB represents an acid.
M represents an alkali metal atom. ) In the hydrocarbon solvent, the salt represented by the formula (1) and the salt represented by the formula (2) are represented in the presence of 0.5 to 5 mol of the polar solvent with respect to 1 mol of the salt represented by the formula (1). A method for producing a salt represented by the formula (3), which comprises a step (a) of reacting with an alkali metal iodide to obtain a salt represented by the formula (3).

(During the ceremony,
A ¹ and A ² independently have a hydrogen atom, a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, and a silyl which may have a substituent. Represents a siroxy group which may have a group or a substituent, or a nitrogen-containing heterocyclic group which may have a substituent together with a nitrogen atom to which A ¹ and A ² are bonded and adjacent to them. Form.
Z represents a divalent aliphatic hydrocarbon group which may have a substituent.
X represents a chlorine atom or a bromine atom.
HB represents an acid.
M represents an alkali metal atom. ) The method according to claim 2, 6 or 7 , wherein the amount of the hydrocarbon solvent is 0.5 to 25 parts by weight with respect to 1 part by weight of the salt represented by the formula (1).