JP2003163031A - ELECTROLYTE, NONAQUEOUS ELECTROCHEMICAL EQUIPMENT AND alpha-SUBSTITUTIONAL OXY-gamma-BUTYROLACTONE DERIVATIVE - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain electrolyte which can acquire high charging efficiency if the electrolyte is used for a nonaqueous electrolyte electrochemical equipment. <P>SOLUTION: The electrolyte in the invention contains α-substitutional oxy-γ- butyrolactone derivative indicated in a following equation (1) (X shows an organic group forming carbonate, thiocarbonate, acetal and ester or ether as well as oxygen atom adjacent to the X in the equation. A γ-butyrolactone ring in the equation may contain a substituent and the several substituents may be bound to form a ring with 1 to 3 carbon atoms composing the γbutyrolactone ring. If the X is the organic group forming the ether with the oxygen atom adjacent to the X, however, the γ-butyrolactone ring in the equation includes at least one substituent besides a X-O-group shown in the equation). <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an electrolytic solution for a non-aqueous electrolytic solution electrochemical device such as a non-aqueous electrolytic solution secondary battery, a non-aqueous electrolytic solution electrochemical apparatus using the electrolytic solution, and the electrolytic solution. The present invention relates to a novel α-substituted oxy-γ-butyrolactone derivative useful as a constituent component.

[0002]

2. Description of the Related Art Non-aqueous electrolyte electrochemical devices using light metals such as lithium as a negative electrode active material (for example, batteries and capacitors for electric double layers) are used in a wide variety of electric and electronic devices. . In particular, the non-aqueous electrolyte secondary battery has a high energy density, and thus has attracted attention as a small-sized and lightweight charge / discharge battery.

Electrolyte solutions used in non-aqueous electrolyte secondary batteries and the like include cyclic carbonic acid esters such as ethylene carbonate and propylene carbonate, chain carbonic acid esters such as dimethyl carbonate and diethyl carbonate, γ-butyrolactone, and the like. Often, a mixture of is used as a solvent. Japanese Patent Laid-Open No. 2001-
No. 185214, non-aqueous electrochemistry containing any one or more compounds selected from the group consisting of ketolactone, cyclic ketoacetal, cyclic hydroxyacetal, hydroxylactone, cyclic borate ester and hydroxyketoester having a specific structure. A device electrolyte is disclosed. However, these conventional electrolytic solutions have not always been sufficiently satisfactory in terms of charge / discharge efficiency and capacity retention rate when used in a non-aqueous electrolytic solution electrochemical device.

[0004]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an electrolytic solution which can obtain a high charge / discharge efficiency when used in a non-aqueous electrolytic solution electrochemical device, and a non-aqueous electrolytic solution including the electrolytic solution. An object is to provide an electrochemical device. Another object of the present invention is to provide an electrolytic solution that can obtain a high capacity retention rate when used in a non-aqueous electrolytic solution electrochemical device, and a non-aqueous electrolytic solution electrochemical device including the electrolytic solution. . Still another object of the present invention is to provide a novel α-substituted oxy-γ-butyrolactone derivative useful as a constituent component of an electrolytic solution.

[0005]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventors have found that an electrolyte containing a specific α-substituted oxy-γ-butyrolactone derivative is used as a non-aqueous electrolyte electrochemical device. It was found that a high charge / discharge efficiency and a high capacity retention rate can be obtained when used for the above, and the present invention has been completed.

That is, the present invention provides the following formula (1):

[Chemical 11] (In the formula, X represents an organic group which forms a carbonate, thiocarbonate, acetal, ester or ether with an adjacent oxygen atom. The γ-butyrolactone ring in the formula may have a substituent, May form a ring with 1 to 3 carbon atoms forming a γ-butyrolactone ring by bonding, provided that when X is an organic group which forms an ether with an adjacent oxygen atom, The γ-butyrolactone ring in the formula provides an electrolytic solution containing an α-substituted oxy-γ-butyrolactone derivative represented by (having at least one substituent other than the X—O— group described in the formula).

The present invention also provides a non-aqueous electrochemical device equipped with the above-mentioned electrolytic solution. This non-aqueous electrochemical device may include at least two electrodes, a separator interposed between the two electrodes, and the above electrolytic solution.

The present invention further provides the following formula (1a)

[Chemical 12] (In the formula, X ¹ is a hydrocarbon group which may have a substituent,
A heterocyclic group which may have a substituent or a nitrogen atom-containing group having a nitrogen atom at the binding site with Y is shown. Y is
Indicates an oxygen atom or a sulfur atom. R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different and represent a hydrogen atom, an optionally substituted hydrocarbon group or a substituted oxycarbonyl group. A plurality of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may combine to form a ring together with 1 or 2 carbon atoms constituting a γ-butyrolactone ring. However, when Y is an oxygen atom and both R ² and R ³ are optionally substituted hydrocarbon groups, R ¹ is a hydrogen atom or an alkyl group, X ¹
Is an alkyl group) α-substituted oxy-γ-
A butyrolactone derivative is provided.

The present invention also provides that X ¹ is (i) the following formula (1a
-1)

[Chemical 13] (In the formula, R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and represent a hydrogen atom, an optionally substituted hydrocarbon group or a substituted oxycarbonyl group. ⁶ , R ⁷ , R
^A plurality of ⁸ , R ⁹ and R ¹⁰ may combine to form a ring together with 1 to 3 carbon atoms constituting the γ-butyrolactone ring. Provided that R ⁹ and R ¹⁰ are groups other than hydrogen atom), (ii) a saturated or unsaturated aliphatic hydrocarbon group, (iii) a hydrocarbon group containing an aryl group, or (iv ) The following formula (1a-2)

[Chemical 14] (In the formula, R ¹¹ and R ¹² are the same or different and each represents a hydrogen atom, an optionally substituted hydrocarbon group, or a substituted oxycarbonyl group. R ¹¹ and R ¹² are bonded to each other. It may be a double bond or a ring) to provide an α-substituted oxy-γ-butyrolactone derivative according to claim 4.

The present invention also provides the following formula (1b)

[Chemical 15] (In the formula, X ² represents a hydrocarbon group which may have a substituent. X ³ and X ⁴ are the same or different and are a hydrogen atom or a hydrocarbon group which may have a substituent. R ¹ ,
R ² , R ³ , R ⁴ and R ⁵ are the same or different and each represent a hydrogen atom, a hydrocarbon group which may have a substituent, or a substituted oxycarbonyl group. R ¹ , R ² , R ³ , R ⁴ and R ⁵
May form a ring together with 1 to 3 carbon atoms forming a γ-butyrolactone ring by combining a plurality of them. However, R ⁴ and R ⁵ are groups other than a hydrogen atom) to provide an α-substituted oxy-γ-butyrolactone derivative.

The present invention also provides the following formula (1c)

[Chemical 16] (In the formula, X^FiveIs a hydrocarbon group which may have a substituent
Show. R¹, R², R³, R ^FourAnd R^FiveAre the same or different
A hydrogen atom, a hydrocarbon group which may have a substituent,
Alternatively, it represents a substituted oxycarbonyl group. R¹, R², R³,
R^FourAnd R^FiveIs a γ-butyrolactone ring formed by combining a plurality of
Forming a ring with 1 to 3 carbon atoms constituting
Good. However, R¹, R², R³, R^FourAnd R^FiveLess of
At least one has a fluorinated hydrocarbon group or substituent
Is an optionally substituted aryl group) α-substituted oxy
Provided are -γ-butyrolactone derivatives.

The present invention further provides the following formula (1d)

[Chemical 17] (In the formula, X⁶Is a hydrocarbon group which may have a substituent
Show. R¹, R², R³, R ^FourAnd R^FiveAre the same or different
A hydrogen atom, a hydrocarbon group which may have a substituent,
Alternatively, it represents a substituted oxycarbonyl group. R¹, R², R³,
R^FourAnd R^FiveIs a γ-butyrolactone ring formed by combining a plurality of
Forming a ring with 1 to 3 carbon atoms constituting
Good. However, R^FourAnd R^FiveIs a non-
Α-substituted oxy represented by (forming an aromatic ring)
Provided are -γ-butyrolactone derivatives.

The present invention also provides the following formula (1e)

[Chemical 18] (In the formula, X ⁷ represents a saturated hydrocarbon group which may have a substituent. R ² , R ³ , R ⁴ and R ⁵ are the same or different and each have a hydrogen atom or a substituent. A hydrocarbon group, which may be
Alternatively, it represents a substituted oxycarbonyl group. R ^2, R ^3, R ⁴ and R ^5, together with 1 to 3 carbon atoms a plurality constitutes a binding to γ- butyrolactone ring may form a ring. However, R ⁴ and R ⁵ are groups other than a hydrogen atom) to provide an α-substituted oxy-γ-butyrolactone derivative.

The present invention also provides the following formula (1f)

[Chemical 19] (In the formula, X⁸Is a hydrocarbon group which may have a substituent
Show. R¹, R², R³, R ^FourAnd R^FiveAre the same or different
A hydrogen atom, a hydrocarbon group which may have a substituent,
Alternatively, it represents a substituted oxycarbonyl group. R¹, R², R³,
R^FourAnd R^FiveIs a γ-butyrolactone ring formed by combining a plurality of
Forming a ring with 1 to 3 carbon atoms constituting
Good. However, R²Is a substituted oxycarbonyl group,
R^FourAnd R^FiveIs a group other than a hydrogen atom) α-
Provided are substituted oxy-γ-butyrolactone derivatives.

The present invention further provides the following formula (1g)

[Chemical 20] (In the formula, X⁹Is a hydrocarbon group which may have a substituent
Show. R¹, R², R³, R ^FourAnd R^FiveAre the same or different
A hydrogen atom, a hydrocarbon group which may have a substituent,
Alternatively, it represents a substituted oxycarbonyl group. R¹, R², R³,
R^FourAnd R^FiveIs a γ-butyrolactone ring formed by combining a plurality of
Forming a ring with 1 to 3 carbon atoms constituting
Good. However, R¹, R^FourAnd R^FiveIs a group other than hydrogen atom
Α-substituted oxy-γ-butyrolactone represented by
Derivatives are provided.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION [α-Substituted oxy-γ-butyrolactone derivative] The electrolytic solution of the present invention contains the α-substituted oxy-γ-butyrolactone derivative represented by the above formula (1).

In the formula (1), X represents a carbonate, a thiocarbonate together with an adjacent oxygen atom shown in the formula,
Indicates an organic group forming an acetal, ester or ether. The organic group includes the following formulas (a), (a ′),
The groups represented by (b), (c) and (d) are included.

[0018] ^{X a -O-C (= O} ) - (a) X a '-S-C (= O) - (a') X b -O-C (X c) (X d) - (b ^{) X e -C (= O)} - (c) X f - (d) ( in the formula, X ^a, X ^{a ',} respectively, which may have a substituent a hydrocarbon group, a substituent A heterocyclic group which may have or a nitrogen atom-containing group which has a nitrogen atom at a binding site with an oxygen atom or a sulfur atom is shown. X ^b , X ^e , X
^f represents a hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent.
X ^c and X ^d each represent a hydrogen atom or a hydrocarbon group which may have a substituent)

The hydrocarbon group in X ^{a and the} like includes an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group and a group in which a plurality of these groups are bonded. Examples of the aliphatic hydrocarbon group include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, decyl and dodecyl groups having 1 to 20 carbon atoms (preferably 1 to 20 carbon atoms). 10) Alkyl group of about 2 to 2 carbon atoms such as vinyl, allyl and 1-butenyl groups
Examples include alkenyl groups having about 20 (preferably 2 to 10); alkynyl groups having about 2 to 20 (preferably 2 to 10) carbon atoms such as ethynyl and propynyl groups.

The alicyclic hydrocarbon group has, for example, a cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl or cyclooctyl group and the like and has about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members). A cycloalkyl group; a cycloalkenyl group having about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members) such as a cyclopentenyl and a cyclohexenyl group; and a bridged cyclic group such as an adamantyl group. Can be mentioned. Examples of the aromatic hydrocarbon group (aryl group) include aromatic hydrocarbon groups having about 6 to 14 (preferably 6 to 10) carbon atoms such as phenyl and naphthyl groups.

The hydrocarbon group in which an aliphatic hydrocarbon group and an alicyclic hydrocarbon group are bonded includes a cycloalkyl-alkyl group such as cyclopentylmethyl, cyclohexylmethyl, 2-cyclohexylethyl group (for example, C _3-20). (Eg, cycloalkyl-C _1-4 alkyl group) and the like. Further, the hydrocarbon group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded to each other includes an aralkyl group (for example, a C _7-18 aralkyl group), an alkyl-substituted aryl group (for example, 1 to
Such as a phenyl group or a naphthyl group substituted with about 4 C _1-4 alkyl groups) and the like.

Preferred hydrocarbon groups are C _1-10 alkyl groups, C _2-10 alkenyl groups, C _2-10 alkynyl groups, C _3-15
Cycloalkyl group, C _6-15 bridged cyclic group, C _6-10 aryl group, C _3-15 cycloalkyl-C _1-4 alkyl group, C
_7-14 Includes aralkyl groups.

The heterocyclic ring forming the heterocyclic group in X ^{a and the} like includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring. Examples of such a heterocycle include heterocycles containing an oxygen atom as a hetero atom (for example, furan, tetrahydrofuran, oxazole, isoxazole, γ
5-membered ring such as butyrolactone, 6-membered ring such as 4-oxo-4H-pyran, tetrahydropyran, morpholine and δ-valerolactone, condensation of benzofuran, isobenzofuran, 4-oxo-4H-chromene, chroman, isochroman, etc. Ring, etc.), a heterocycle containing a sulfur atom as a hetero atom (for example, a 5-membered ring such as thiophene, thiazole, isothiazole and thiadiazole, a 6-membered ring such as 4-oxo-4H-thiopyran, a condensed ring such as benzothiophene, etc. ), A heterocycle containing a nitrogen atom as a hetero atom (for example, a 5-membered ring such as pyrrole, pyrrolidine, pyrazole, imidazole and triazole, a 6-membered ring such as pyridine, pyridazine, pyrimidine, pyrazine, piperidine and piperazine, indole, indoline, Quinoline, acridine, naphth Lysine, quinazoline, other condensed rings purine) and the like.

Examples of the substituent which the above-mentioned hydrocarbon group or heterocyclic group may have include halogen atoms such as fluorine, chlorine and bromine atoms; hydroxyl group; methoxy, ethoxy, propoxy, isopropoxy and butoxy. , Alkoxy groups such as hexyloxy, octyloxy and decyloxy groups (preferably C _1-10 alkoxy groups, more preferably C _1-4 alkoxy groups), cycloalkyloxy groups such as cyclopropyloxy, cyclopentyloxy and cyclohexyloxy groups. A substituted oxy group such as an aryloxy group such as a phenyloxy group, an aralkyloxy group such as a benzyloxy group, an acyloxy group (preferably a C _1-7 acyloxy group) such as acetyloxy and benzoyloxy group; a carboxyl group; methoxycarbonyl , Ethoxycarbonyl, Alkoxycarbonyl groups such as propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl groups (preferably C _1-4 alkoxycarbonyl groups), cycloalkyloxycarbonyl groups such as cyclohexyloxycarbonyl groups, aryloxycarbonyl groups such as phenyloxycarbonyl groups, A substituted oxycarbonyl group such as an aralkyloxycarbonyl group such as a benzyloxycarbonyl group; a carbamoyl group;
Substituted carbamoyl group such as mono- or dialkyl-substituted carbamoyl group (preferably mono- or di-C _1-4 alkyl-substituted carbamoyl group); amino group; mono- or dialkylamino group (preferably mono- or di-C _1-4 alkylamino group) ), A substituted amino group such as cyclic amino group such as piperidino group; an aliphatic acyl group such as formyl, acetyl, propionyl, butyryl, isobutyryl, octanoyl group (preferably C _1-10 aliphatic acyl group, more preferably C
_1-4 aliphatic acyl group), acyl group such as aromatic acyl group such as benzoyl group; cyano group; nitro group; oxo group; sulfuric acid group; sulfuric acid ester group; methyl, ethyl, propyl, isopropyl, butyl, Isobutyl, s-butyl,
Alkyl group such as t-butyl group (preferably C _1-4 alkyl group); Alkenyl group such as vinyl or allyl group (preferably C _2-4 alkenyl group); Alkynyl group such as propynyl group (preferably C _{2-) 4} alkynyl group); cycloalkyl group such as cyclohexyl group; aryl group such as phenyl group; aralkyl group such as benzyl group; trifluoromethyl, 2,2,2-trifluoroethyl, 3,3,3
Examples thereof include a haloalkyl group such as a 3-trifluoropropyl group (preferably a C _1-4 haloalkyl group); and a heterocyclic group such as a pyridyl group.

Examples of the nitrogen atom-containing group having a nitrogen atom at the binding site with the oxygen atom or the sulfur atom in X ^a and X ^{a ′} include, for example, a substituted or unsubstituted amino group, a substituted or unsubstituted carbamoyl group and a nitro group. , Nitroamido group,
Examples thereof include a nitroso group, an organic group represented by the above formula (1a-2), and a group having a nitrogen atom of a heterocycle containing a nitrogen atom such as pyrrole and piperidine at a bonding site. The details of the organic group represented by the formula (1a-2) will be described later.

As X ^a , X ^{a ′} , X ^b and X ^f , in particular, C
_1-10 alkyl group (especially C _1-5 alkyl group), C _2-10
Alkenyl group, C _2-10 alkynyl group, C _3-15 cycloalkyl group, C _6-15 bridged cyclic group, C _6-10 aryl group, C
_{A 3-15} cycloalkyl-C _1-4 alkyl group, a C _7-14 aralkyl group and the like are preferable. Further, as X ^a and X ^{a ′} , a nitrogen atom-containing group represented by the above formula (1a-2) and the like are also preferable.

As X ^c and X ^d , hydrogen atom, C
_1-10 alkyl group (especially C _1-5 alkyl group), C _2-10
Alkenyl group, C _2-10 alkynyl group, C _3-15 cycloalkyl group, C _6-15 bridged cyclic group, C _6-10 aryl group, C
_{A 3-15} cycloalkyl-C _1-4 alkyl group, a C _7-14 aralkyl group and the like are preferable.

X ^e is a hydrocarbon group which may have a substituent, particularly a C _1-10 alkyl group (especially C _1-5).
Alkyl group), C _2-10 alkenyl group, C _2-10 alkynyl group, C _3-15 cycloalkyl group, C _6-15 bridged cyclic group, substituent (for example, halogen atom, C _1-4 alkoxy group) , C
_1-4 alkoxycarbonyl group, nitro group, C _1-4 alkyl group, C _1-4 haloalkyl group, etc.)
_6-10 aryl group, C _{3-1 5} cycloalkyl -C _1-4 alkyl group, C _{7 - 14} aralkyl group, C _1-10 such haloalkyl groups (especially C _1-5 haloalkyl group).

The γ-butyrolactone ring in the formula (1) may have a substituent. Examples of the substituent include a hydrocarbon group which may have a substituent, a halogen atom, a hydroxyl group, a substituted oxy group, a carboxyl group, a substituted oxycarbonyl group, a carbamoyl group, a substituted carbamoyl group, an amino group and a substituted group. Examples thereof include an amino group, an acyl group, a cyano group, a nitro group, an oxo group, a sulfuric acid group, a sulfuric acid ester group, and a heterocyclic group which may have a substituent.

Hydrocarbon group which may have the above-mentioned substituent
“Hydrocarbon group” in is methyl, ethyl, propyl
, Isopropyl, butyl, isobutyl, sec-butyl,
t-butyl, pentyl, hexyl, octyl, decyl,
C such as dodecyl group_1-20Alkyl group (preferably C_1-10
An alkyl group, more preferably C_1-5Alkyl group);
Nyl, allyl, isopropenyl, 1-butenyl, 1-o
C such as octenyl and 7-octenyl group_2-20Alkenyl group
(Preferably C_2-10Alkenyl group, more preferably C
_2-5Alkenyl group); ethynyl, 1-propynyl group, etc.
C_2-20Alkynyl group (preferably C_2-10Alkynyl
Group, more preferably C_2-5Alkynyl group); cyclop
Ropil, cyclopentyl, cyclohexyl, cyclooctyl
3 to 2 such as tyl, cyclododecyl and cyclododecyl group
0-membered cycloalkyl group (preferably 3- to 6-membered cycloalkyl group)
Alkyl group); cyclopentenyl, cyclohexenyl group
3- to 20-membered cycloalkenyl groups such as
~ 6-membered cycloalkenyl group); such as adamantyl group
6-20 member bridged cyclic group (preferably 6-15 member bridge)
Hooked cyclic group); C such as phenyl or naphthyl group_6-15Ants
Group (preferably C _6-10Aryl group); benzyl, 2
C such as -phenylethyl and 1-phenylethyl groups_7-15
Includes aralkyl groups and the like.

Examples of the substituent which these hydrocarbon groups may have include those exemplified as the substituents which the hydrocarbon group or the heterocyclic group in X ^{a and the} like may have. To be Preferred examples of the hydrocarbon group having a substituent include, for example, 2-fluorophenyl, 2-chlorophenyl, 3-fluorophenyl, 3-chlorophenyl, 4-fluorophenyl, 4-chlorophenyl, 4-
Methoxyphenyl, 4-nitrophenyl, 4-methoxycarbonylphenyl, 4-nitrophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl,
Has a substituent such as a halogen atom, C _1-4 alkoxy group, C _1-4 alkoxycarbonyl group, nitro group, C _1-4 alkyl group, C _1-4 haloalkyl group, such as 4-trifluoromethylphenyl C _6-10 aryl group; trifluoromethyl, 2,2,2-trifluoroethyl, 3,3
Examples thereof include C _1-10 haloalkyl groups such as 3-trifluoropropyl group (especially C _1-5 haloalkyl groups).

The halogen atom as the substituent of the γ-butyrolactone ring includes fluorine, chlorine, bromine atom and the like. Examples of the substituted oxy group include alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, hexyloxy, octyloxy, and decyloxy groups (preferably C _1-10 alkoxy group, more preferably C _1-4 alkoxy group). ); Cycloalkyloxy groups such as cyclopropyloxy, cyclopentyloxy and cyclohexyloxy groups; aryloxy groups such as phenyloxy groups; aralkyloxy groups such as benzyloxy groups; acyloxy groups such as acetyloxy and benzoyloxy groups (preferably C _1-7 acyloxy group) and the like. Examples of the substituted oxycarbonyl group include alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl and butoxycarbonyl groups (preferably C _1-4 alkoxycarbonyl groups); cycloalkyl such as cyclohexyloxycarbonyl groups. An oxycarbonyl group; an aryloxycarbonyl group such as a phenyloxycarbonyl group; and an aralkyloxycarbonyl group such as a benzyloxycarbonyl group. Examples of the substituted carbamoyl group include mono- or dialkyl-substituted carbamoyl groups such as methylcarbamoyl and dimethylcarbamoyl groups (preferably mono- or di-C _1-4 alkyl-substituted carbamoyl groups). As the substituted amino group,
Examples thereof include mono- or dialkylamino groups such as N-methylamino and N, N-dimethylamino groups (preferably mono- or di-C _1-4 alkylamino groups); cyclic amino groups such as piperidino groups. The acyl groups include formyl, acetyl, propionyl, butyryl, isobutyryl, aliphatic acyl group (preferably C _1-10 aliphatic acyl group, more preferably C _1-4 aliphatic acyl group), such as octanoyl group; a benzoyl group And an aromatic acyl group. Examples of the heterocyclic group which may have a substituent include the same groups as the heterocyclic group which may have a substituent in the above X ^a and the like.

As the substituent of the γ-butyrolactone ring, among the above, a hydrocarbon group which may have a substituent [for example, a C _1-10 alkyl group (especially C _1-5 alkyl group); C _1-10 haloalkyl group (especially C _1-5 haloalkyl group); C _2-1 0 alkenyl group (especially C _2-5 alkenyl group); 3-20 membered cycloalkyl group (preferably 3 to
6-membered cycloalkyl group); an aryl group; a halogen atom, C _1-4 alkoxy groups, C _{1 -4} alkoxycarbonyl group, at least selected from a nitro group, C _1-4 alkyl and C _1-4 haloalkyl group C having one substituent
_6-10 aryl group; C _7-15 aralkyl group, cycloalkyl group], hydroxyl group, C _1-10 alkoxy group (especially C
_1-4 alkoxy group), C _1-7 acyloxy group, carboxyl group, substituted oxycarbonyl group (for example, C _1-4 alkoxycarbonyl group), C _1-10 aliphatic acyl group, aromatic acyl group, cyano group , Oxo group and the like are preferable.

A plurality of substituents on the γ-butyrolactone ring may be bonded to each other to form a ring together with 1 to 3 carbon atoms constituting the γ-butyrolactone ring. Such rings include non-aromatic and aromatic rings. As the non-aromatic ring, for example, a cyclopropane ring, a cyclopentane ring, a cyclohexane ring, a cyclooctane ring or the like
20-membered cycloalkane ring (preferably 3- to 6-membered cycloalkane ring), cyclopentene ring, cyclohexene ring, and other 3- to 20-membered cycloalkene ring (preferably 3 to 6-membered cycloalkane ring)
6-membered cycloalkene ring), adamantane ring, etc.
20-member bridge ring (preferably 6-15 member bridge ring)
And non-aromatic heterocycles such as tetrahydrofuran ring, tetrahydrothiophene ring, pyrrolidine ring, piperazine ring and morpholine ring. Examples of the aromatic ring include an aromatic carbocycle such as a benzene ring and an aromatic heterocycle such as a furan ring, a thiophene ring and a pyridine ring. Among these, non-aromatic rings, especially non-aromatic carbocycles are preferable.

Α-Substituted oxy-γ-represented by the formula (1)
The γ-butyrolactone ring in the butyrolactone derivative preferably has at least one hydrogen atom at the β-position.

Α-Substituted oxy-γ-represented by the formula (1)
Among the butyrolactone derivatives, preferred compounds include a compound represented by the formula (1a), a compound represented by the formula (1b), a compound represented by the formula (1c), and a compound represented by the formula (1d). , A compound represented by the formula (1e), a compound represented by the formula (1f) and a compound represented by the formula (1g). These compounds are novel compounds, and when used as a constituent component of the electrolytic solution of the non-aqueous electrochemical device, particularly high charge / discharge efficiency and capacity retention rate can be obtained.

Other preferred compounds include α-substituted oxy-γ-, such as α-methoxycarbonyloxy-γ-butyrolactone, α-methoxymethoxy-γ-butyrolactone and α-acetyloxy-γ-butyrolactone.
Butyrolactone; α-methoxycarbonyloxy-β-
Methyl-γ-butyrolactone, α-methoxymethoxy-
β-methyl-γ-butyrolactone, α-acetyloxy-β-methyl-γ-butyrolactone, α-methoxy-β
Α-substituted oxy-, such as methyl-γ-butyrolactone
β-methyl-γ-butyrolactone; α-methoxycarbonyloxy-β, β-dimethyl-γ-butyrolactone,
α-methoxymethoxy-β, β-dimethyl-γ-butyrolactone, α-acetyloxy-β, β-dimethyl-γ
-Butyrolactone, α-methoxy-β, β-dimethyl-
Examples include α-substituted oxy-β, β-dimethyl-γ-butyrolactone such as γ-butyrolactone. When these compounds are used as a constituent of the electrolyte of a non-aqueous electrochemical device, they have the advantages of high charge / discharge efficiency and capacity retention, and also of being inexpensively manufactured.

[Compound represented by Formula (1a)] The above formula (1
In a), X ¹ represents a hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a nitrogen atom-containing group which has a nitrogen atom at the binding site with Y. Show. Y
Represents an oxygen atom or a sulfur atom. R ¹ , R ² , R ³ , R ⁴
And R ⁵ are the same or different and each represents a hydrogen atom, a hydrocarbon group which may have a substituent, or a substituted oxycarbonyl group. A plurality of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may combine to form a ring together with 1 or 2 carbon atoms constituting a γ-butyrolactone ring. However, when Y is an oxygen atom and both R ² and R ³ are hydrocarbon groups which may have a substituent, R ¹ is a hydrogen atom or an alkyl group, and X ¹ is an alkyl group.

Examples of the hydrocarbon group which may have a substituent in X ¹ include the same ones as those described above as the hydrocarbon group which may have ^a substituent in X ^a . X ¹ is, in particular, (i) the above formula (1a-1)
An organic group represented by, (ii) a saturated or unsaturated aliphatic hydrocarbon group, (iii) a hydrocarbon group containing an aryl group, (iv) an organic group represented by the formula (1a-2) and the like are preferable. .

In the above formula (1a-1), R ⁶ , R ⁷ ,
R ⁸ , R ⁹ and R ¹⁰ are the same or different and each represents a hydrogen atom, a hydrocarbon group which may have a substituent, or a substituted oxycarbonyl group. A plurality of R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are combined to form a γ-butyrolactone ring.
It may form a ring with carbon atoms. However, R
⁹ and R ¹⁰ are groups other than hydrogen atom.

The hydrocarbon group which may have a substituent, the substituted oxycarbonyl group, and preferred groups among them in R ^{6 and the} like have a γ-butyrolactone ring in the above formula (1). Examples of the substituent that may be present include the same groups as the “hydrocarbon group which may have a substituent” and the “substituted oxycarbonyl group” illustrated as examples. Also,
Examples of the ring formed by combining a plurality of R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ together with 1 to 3 carbon atoms constituting the γ-butyrolactone ring, and a preferable ring among them are: Examples of the ring are the same as those exemplified as the ring formed with 1 to 3 carbon atoms constituting the γ-butyrolactone ring by bonding a plurality of substituents on the γ-butyrolactone ring in the above formula (1). .

Specific examples of the organic group (i) represented by the formula (1a-1) include γ, γ-dimethyl-γ-butyrolactone-
α-yl, γ, γ-diethyl-γ-butyrolactone-α
Examples include organic groups such as -yl, β, γ, γ-trimethyl-γ-butyrolactone-α-yl, β-methyl-γ, γ-diethyl-γ-butyrolactone-α-yl groups.

The saturated or unsaturated aliphatic hydrocarbon group (i
Specific examples of i) include C _1-10 such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl and dodecyl groups, particularly C _1-5 linear saturated aliphatic hydrocarbon group, and Isopropyl, isobutyl, sec-butyl,
C _3-10 such as t-butyl group, especially C _3-5 branched saturated aliphatic hydrocarbon group; alkenyl group such as vinyl, allyl, 1-butenyl, 1-octenyl, 7-octenyl group, ethynyl or 1- C such as alkynyl group such as propynyl group
_2-10 linear unsaturated aliphatic groups, and C _3-10 branched unsaturated aliphatic groups such as isopropenyl.

Hydrocarbon group containing the aryl group (iii)
Specific examples of C _6-10 include phenyl and naphthyl groups.
Aryl group; C _7-14 aralkyl group such as benzyl, 2-phenylethyl, 1-phenylethyl group and the like can be mentioned.

In the above formula (1a-2), R ¹¹ and R
^12's are the same or different and each represents a hydrogen atom, a hydrocarbon group which may have a substituent, or a substituted oxycarbonyl group. R ¹¹ and R ¹² may combine with each other to form a double bond or an aromatic or non-aromatic ring.

The hydrocarbon group which may have a substituent in R ¹¹ and R ¹² , a substituted oxycarbonyl group, and preferable groups among them are the γ-butyrolactone ring in the above formula (1). The same groups as the "hydrocarbon group optionally having substituent (s)" and "substituted oxycarbonyl group" exemplified as the substituent optionally having are exemplified.
The ring formed by R ¹¹ and R ¹² bonded to each other, and a preferred ring among them is a γ-butyrolactone ring formed by bonding a plurality of substituents on the γ-butyrolactone ring in the above formula (1). The same rings as those exemplified as the ring formed with the constituent 1 to 3 carbon atoms can be mentioned.

Specific examples of the organic group (iv) represented by the above formula (1a-2) include ethylideneamino group, propylideneamino group, isopropylideneamino group, cyclohexylideneamino group and benzylideneamino group. Is mentioned.

The hydrocarbon group which may have a substituent in R ¹ , R ² , R ³ , R ⁴ and R ⁵ , a substituted oxycarbonyl group, and preferable groups among them are those represented by the above formula (1 The same groups as the "hydrocarbon group which may have a substituent" and the "substituted oxycarbonyl group" which are exemplified as the substituent which the γ-butyrolactone ring in () may have. Further, as a ring formed by combining a plurality of R ¹ , R ² , R ³ , R ⁴ and R ⁵ together with 1 or 2 carbon atoms constituting a γ-butyrolactone ring, and preferable rings among them Is a ring similar to the ring exemplified as the ring formed with 1 to 3 carbon atoms constituting the γ-butyrolactone ring by bonding a plurality of substituents on the γ-butyrolactone ring in the above formula (1). Can be mentioned.

As a typical example of the compound represented by the formula (1a), bis (γ, γ-dimethyl-γ-butyrolactone-
compounds in which X ¹ is an organic group (i) represented by the formula (1a-1), such as α-yl) carbonate; α-methoxycarbonyloxy-γ, γ-dimethyl-γ-butyrolactone, α-methoxycarbonyl Oxy-β, γ, γ-trimethyl-γ-butyrolactone, β-trifluoromethyl-α-methoxycarbonyloxy-γ, γ-dimethyl-
γ-butyrolactone, α-methoxycarbonyloxy-
γ, γ-dimethyl-β-phenyl-γ-butyrolactone, β-methoxycarbonyl-α-methoxycarbonyloxy-γ, γ-dimethyl-γ-butyrolactone, 3-
Methoxycarbonyloxy-2-oxo-1-oxaspiro [4.5] decane, α-methoxycarbonyloxy-γ-propyl-γ-butyrolactone, α-methoxycarbonyloxy-α, γ, γ-trimethyl-γ-butyrolactone, α-ethoxycarbonyloxy-γ, γ-dimethyl-γ-butyrolactone, α- (methylthio) carbonyloxy-γ-butyrolactone, α- (methylthio) carbonyloxy-γ, γ-dimethyl-γ-butyrolactone, α- (ethylthio ) Carbonyloxy-γ-
Compounds in which X ¹ is a linear saturated aliphatic hydrocarbon group, such as butyrolactone and α- (ethylthio) carbonyloxy-γ, γ-dimethyl-γ-butyrolactone, α- (tert
-Butyloxycarbonyloxy) -γ, γ-dimethyl-γ-butyrolactone, α- (2-methylpropyloxycarbonyloxy) -γ, γ-dimethyl-γ-butyrolactone, and other branched saturated aliphatic hydrocarbon groups. Compound, α- (2-propynyloxycarbonyloxy)-
γ, γ-dimethyl-γ-butyrolactone, α-vinyloxycarbonyloxy-γ, γ-dimethyl-γ-butyrolactone, α-allyloxycarbonyloxy-γ, γ
-Dimethyl-γ-butyrolactone, α- (2-propynylthiocarbonyloxy) -γ, γ-dimethyl-γ-butyrolactone, and other compounds in which X ¹ is a linear unsaturated aliphatic hydrocarbon group, α-isopropenyloxy Compounds in which X ¹ is a saturated or unsaturated aliphatic hydrocarbon group (ii), such as compounds having a branched unsaturated aliphatic hydrocarbon group such as carbonyloxy-γ, γ-dimethyl-γ-butyrolactone; α-
Phenoxycarbonyloxy-γ, γ-dimethyl-γ-
Butyrolactone, α- (phenylthio) carbonyloxy-γ, γ-dimethyl-γ-butyrolactone, α-benzyloxycarbonyloxy-γ, γ-dimethyl-γ-
Butyrolactone, α-benzylthiocarbonyloxy-
Compounds in which X ¹ is a hydrocarbon group (iii) containing an aryl group such as γ, γ-dimethyl-γ-butyrolactone; α-benzylideneaminooxycarbonyloxy-γ, γ-dimethyl-γ-butyrolactone, α-cyclohe Xylidene aminooxycarbonyloxy-γ, γ-dimethyl-γ
Examples include an organic group (iv) in which X ^{1 of} butyrolactone or the like is represented by the above formula (1a-2).

Α-substituted oxy-γ-represented by the formula (1a)
The butyrolactone derivative is, for example, a compound represented by the following formula (2) with a corresponding α-hydroxy-γ-butyrolactone derivative.

[Chemical 21] (In the formula, X ¹ is the same as above. Y represents an oxygen atom or a sulfur atom. Z ¹ represents a halogen atom), and a haloformic acid (thio) ester derivative represented by the presence of a base, if necessary. It can be produced by reacting under.

Particularly, the α-substituted oxy-γ-butyrolactone derivative in which X ¹ is the organic group (i) represented by the above formula (1a-1) is, for example, the corresponding α-hydroxy-γ-butyrolactone derivative. , The following formula (2a)

[Chemical formula 22] (Wherein Z ¹ and Z ² are the same or different and each represents a halogen atom or a 1-imidazolyl group),
It can also be produced by reacting in the presence of a base, if necessary. Further, the α-substituted oxy-γ-butyrolactone derivative in which X ¹ is the organic group (iv) represented by the formula (1a-2) is, for example, a corresponding α-hydroxy-γ-butyrolactone derivative and the following formula: (2b)

[Chemical formula 23] (Wherein R ¹¹ , R ¹² and Y are the same as above) and the compound represented by the above formula (2a) may be reacted in the presence of a base, if necessary. Can be manufactured.

Examples of the halogen atom in Z, Z ¹ and Z ² include chlorine, bromine and iodine atoms. The base may be either an organic base or an inorganic base, and examples thereof include tertiary amines such as triethylamine and N, N-diisopropylethylamine; nitrogen-containing aromatic heterocyclic compounds such as pyridine; lithium diisopropylamide. , An organic metal compound containing an alkali metal such as butyl lithium and sodium ethoxide; an alkali metal such as sodium; an alkali metal hydride such as sodium hydride; an alkali metal carbonate or hydrogen carbonate such as sodium carbonate and sodium hydrogen carbonate Is mentioned.

The reaction is usually performed in an organic solvent. Examples of the organic solvent include hydrocarbons such as hexane, benzene, and toluene; halogenated hydrocarbons such as dichloromethane and dichloroethane; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran, and 1,4-dioxane; esters such as ethyl acetate; Ketones such as acetone; nitriles such as acetonitrile and benzonitrile; amides such as N, N-dimethylformamide;
And mixed solvents thereof.

The amounts of the haloformic acid (thio) ester derivative represented by the formula (2) and the base are respectively 1 mol of the α-hydroxy-γ-butyrolactone derivative corresponding to the compound of the formula (1a). For example, it is about 0.8 to 5 mol. The reaction temperature can be appropriately selected depending on the type of reaction components, but is usually in the range of about -10 ° C to 100 ° C.

After completion of the reaction, the reaction product can be separated and purified by a separating means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography or a combination thereof. In addition, α-hydroxy-corresponding to the compound of formula (1a) used as a reaction raw material
The γ-butyrolactone derivative can be obtained by a known method, for example, W
It can be obtained by the method described in O00 / 35835 or a method analogous thereto.

[Compound represented by Formula (1b)] The above formula (1
In b), X ² represents a hydrocarbon group which may have a substituent. X ³ and X ⁴ are the same or different and each represents a hydrogen atom or a hydrocarbon group which may have a substituent.
R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different and represent a hydrogen atom, an optionally substituted hydrocarbon group or a substituted oxycarbonyl group. ^{R 1, R 2, R 3} , R 4 and R ^5, may form a ring with 1-3 carbon atoms plurality constitutes a binding to γ- butyrolactone ring. However, R ⁴ and R ⁵ are groups other than hydrogen atom.

The hydrocarbon group which may have a substituent in X ² , X ³ and X ⁴ includes the hydrocarbon group which may have a substituent in the above X ^b , X ^c and X ^d . The same thing as what was described is mentioned. X ² is particularly a C _1-10 alkyl group (particularly a C _1-5 alkyl group),
C _2-10 alkenyl group, C _2-10 alkynyl group, C _3-15 cycloalkyl group, C _6-15 bridged cyclic group, C _6-10 aryl group, C _3-15 cycloalkyl-C _1-4 Alkyl group, C _7-14
Aralkyl groups and the like are preferable. Further, as X ³ and X ⁴ , a hydrogen atom, a C _1-10 alkyl group (especially C
_1-5 alkyl group), C _{2 -10} alkenyl group, C _2-10 alkynyl, C _3-15 cycloalkyl, C _6-15 bridge over cyclic group, C _6-10 aryl group, C _3-15 Cycloalkyl-C _1-4
Such as an alkyl group, C _{7-1 4} aralkyl group are preferred.

The hydrocarbon group which may have a substituent in R ¹ , R ² , R ³ , R ⁴ and R ⁵ , a substituted oxycarbonyl group, and a preferable group thereof are those represented by the above formula (1 The same groups as the "hydrocarbon group which may have a substituent" and the "substituted oxycarbonyl group" which are exemplified as the substituent which the γ-butyrolactone ring in () may have. Further, as a ring formed by combining a plurality of R ¹ , R ² , R ³ , R ⁴ and R ⁵ together with 1 to 3 carbon atoms constituting a γ-butyrolactone ring, and preferable rings among them Is a ring similar to the ring exemplified as the ring formed with 1 to 3 carbon atoms constituting the γ-butyrolactone ring by bonding a plurality of substituents on the γ-butyrolactone ring in the above formula (1). Can be mentioned.

As a typical example of the compound represented by the formula (1b), α-methoxymethoxy-γ, γ-dimethyl-γ-
Butyrolactone, α-methoxymethoxy-β, γ, γ-
Trimethyl-γ-butyrolactone, β-trifluoromethyl-α-methoxymethoxy-γ, γ-dimethyl-γ-
Butyrolactone, α-methoxymethoxy-γ, γ-dimethyl-β-phenyl-γ-butyrolactone, β-methoxycarbonyl-α-methoxymethoxy-γ, γ-dimethyl-γ-butyrolactone, 3-methoxymethoxy-2-
Oxo-1-oxaspiro [4.5] decane, α-methoxymethoxy-α, γ, γ-trimethyl-γ-butyrolactone, α-ethoxymethoxy-γ, γ-dimethyl-γ
-Butyrolactone, α- (1-methoxyethoxy)-
γ, γ-dimethyl-γ-butyrolactone and the like can be mentioned.

Α-substituted oxy-γ-represented by formula (1b)
The butyrolactone derivative is, for example, a compound represented by the following formula (3) with a corresponding α-hydroxy-γ-butyrolactone derivative.

[Chemical formula 24] (In the formula, X ² , X ³ , X ⁴ , and Z are the same as above), and can be produced by reacting with a substituted oxyalkyl halide derivative (halogen atom-containing ether compound) in the presence of a base. As the base, the same bases as in the case of the compound of the above formula (1a) can be used.

The reaction is usually carried out in an organic solvent. As the organic solvent, the same solvent as in the case of the compound of the above formula (1a) can be used. The amounts of the substituted oxyalkyl halide derivative represented by the formula (3) and the base are respectively calculated by the formula (1b)
The amount is, for example, about 0.8 to 5 mol, based on 1 mol of the α-hydroxy-γ-butyrolactone derivative corresponding to the compound (1). The reaction temperature can be appropriately selected depending on the type of reaction components, but is usually in the range of about -10 ° C to 100 ° C.

After completion of the reaction, the reaction product can be separated and purified by a separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination thereof. In addition, α-hydroxy-corresponding to the compound of the formula (1b) used as a reaction raw material
The γ-butyrolactone derivative can be obtained by a known method, for example, W
It can be obtained by the method described in O00 / 35835 or a method analogous thereto.

[Compound represented by Formula (1c)] The above formula (1
In c), X ⁵ represents a hydrocarbon group which may have a substituent. R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different and represent a hydrogen atom, an optionally substituted hydrocarbon group or a substituted oxycarbonyl group. R ¹ , R ² , R
^A plurality of ³ , R ⁴ and R ⁵ may combine to form a ring together with 1 to 3 carbon atoms constituting the γ-butyrolactone ring. However, at least one of R ¹ , R ² , R ³ , R ⁴ and R ⁵ is a fluorinated hydrocarbon group or an aryl group which may have a substituent.

X^FiveOptionally substituted carbon
As the hydrogen halide group, the above X^eHaving a substituent in
The same as those described as the hydrocarbon group which may be
Can be mentioned. X^FiveAs, in particular, C_1-10Alkyl group
(Especially C_1-5Alkyl group), C _2-10An alkenyl group,
C_2-10Alkynyl group, C_3-15Cycloalkyl group, C_6-15
Bridged cyclic group, substituent (for example, halogen atom, C_1-4
Alkoxy group, C_1-4Alkoxycarbonyl group, nitro
Base, C_1-4Alkyl group, C_1-4Haloalkyl group etc.)
C which may be_6-10Aryl group, C_3-15Cycloalk
R-C_1-4Alkyl group, C_7-14Aralkyl group, C_1-10Ha
Lower alkyl group (especially C_1-5Haloalkyl group) etc.
preferable.

The hydrocarbon group which may have a substituent in R ¹ , R ² , R ³ , R ⁴ and R ⁵ , a substituted oxycarbonyl group, and a preferable group thereof are those represented by the above formula (1 The same groups as the "hydrocarbon group which may have a substituent" and the "substituted oxycarbonyl group" which are exemplified as the substituent which the γ-butyrolactone ring in () may have. Further, as a ring formed by combining a plurality of R ¹ , R ² , R ³ , R ⁴ and R ⁵ together with 1 to 3 carbon atoms constituting a γ-butyrolactone ring, and preferable rings among them Is a ring similar to the ring exemplified as the ring formed with 1 to 3 carbon atoms constituting the γ-butyrolactone ring by bonding a plurality of substituents on the γ-butyrolactone ring in the above formula (1). Can be mentioned.

The fluorinated hydrocarbon group for R ¹ , R ² , R ³ , R ⁴ and R ⁵ is, for example, trifluoromethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 3,3. , 3-trifluoropropyl, perfluoropropyl group and the like. Examples of the aryl group which may have a substituent include, for example, phenyl,
Naphthyl, 2-chlorophenyl, 2-fluorophenyl, 3-chlorophenyl, 3-fluorophenyl, 4-
Halogen atom such as chlorophenyl, 4-fluorophenyl, 4-methoxyphenyl, 4-methoxycarbonylphenyl, 4-nitrophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-trifluoromethylphenyl group , C _1-4 alkoxy group, C
Examples thereof include a C _6-10 aryl group having at least one substituent selected from a _1-4 alkoxycarbonyl group, a nitro group, a C _1-4 alkyl group and a C _1-4 haloalkyl group.

As a typical example of the compound represented by the formula (1c), α-acetyloxy-β-trifluoromethyl-
γ, γ-dimethyl-γ-butyrolactone, α-acetyloxy-γ- (3,3,3-trifluoropropyl)-
γ-butyrolactone, α-acetyloxy-β-trifluoromethyl-α, γ, γ-trimethyl-γ-butyrolactone, β-trifluoromethyl-γ, γ-dimethyl-
α-propionyloxy-γ-butyrolactone, α-acetyloxy-γ, γ-dimethyl-β-phenyl-γ-
Butyrolactone, α-acetyloxy-γ-phenyl-
γ-butyrolactone, α-acetyloxy-α, γ, γ
-Trimethyl-β-phenyl-γ-butyrolactone,
γ, γ-dimethyl-β-phenyl-α-propionyloxy-γ-butyrolactone and the like can be mentioned.

Α-substituted oxy-γ-represented by the formula (1c)
The butyrolactone derivative is, for example, a compound represented by the following formula (4) with a corresponding α-hydroxy-γ-butyrolactone derivative.

[Chemical 25] It can be produced by reacting an acyl halide derivative represented by the formula (wherein X ⁵ and Z are the same as above) in the presence of a base. As the base, the same bases as in the case of the compound of the above formula (1a) can be used.

The reaction is usually performed in an organic solvent. As the organic solvent, the same solvent as in the case of the compound of the above formula (1a) can be used. The amount of the acyl halide derivative represented by the formula (4) and the base used is, for example, 0.8 to 5 relative to 1 mol of the α-hydroxy-γ-butyrolactone derivative corresponding to the compound of the formula (1c). It is about molar. The reaction temperature can be appropriately selected depending on the type of reaction components, but is usually in the range of about -10 ° C to 100 ° C.

After completion of the reaction, the reaction product can be separated and purified by a separating means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination thereof. In addition, α-hydroxy-corresponding to the compound of formula (1c) used as a reaction raw material
The γ-butyrolactone derivative can be obtained by a known method, for example, W
It can be obtained by the method described in O00 / 35835 or a method analogous thereto.

[Compound Represented by Formula (1d)] The above formula (1
In d), X ⁶ represents a hydrocarbon group which may have a substituent. R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different and represent a hydrogen atom, an optionally substituted hydrocarbon group or a substituted oxycarbonyl group. R ¹ , R ² , R
^A plurality of ³ , R ⁴ and R ⁵ may combine to form a ring together with 1 to 3 carbon atoms constituting the γ-butyrolactone ring. However, R ⁴ and R ⁵ form a non-aromatic ring together with adjacent carbon atoms.

X⁶Optionally substituted carbon
As the hydrogen halide group, the above X^eHaving a substituent in
The same as those described as the hydrocarbon group which may be
Can be mentioned. X⁶As, in particular, C_1-10Alkyl group
(Especially C_1-5Alkyl group), C _2-10An alkenyl group,
C_2-10Alkynyl group, C_3-15Cycloalkyl group, C_6-15
Bridged cyclic group, substituent (for example, halogen atom, C_1-4
Alkoxy group, C_1-4Alkoxycarbonyl group, nitro
Base, C_1-4Alkyl group, C_1-4Haloalkyl group etc.)
C which may be_6-10Aryl group, C_3-15Cycloalk
R-C_1-4Alkyl group, C_7-14Aralkyl group, C_1-10Ha
Lower alkyl group (especially C_1-5Haloalkyl group) etc.
preferable.

The hydrocarbon group which may have a substituent in R ¹ , R ² , R ³ , R ⁴ and R ⁵ , a substituted oxycarbonyl group, and preferable groups among them are those represented by the above formula (1 The same groups as the "hydrocarbon group which may have a substituent" and the "substituted oxycarbonyl group" which are exemplified as the substituent which the γ-butyrolactone ring in () may have. Further, as a ring formed by combining a plurality of R ¹ , R ² , R ³ , R ⁴ and R ⁵ together with 1 to 3 carbon atoms constituting a γ-butyrolactone ring, and preferable rings among them Is a ring similar to the ring exemplified as the ring formed with 1 to 3 carbon atoms constituting the γ-butyrolactone ring by bonding a plurality of substituents on the γ-butyrolactone ring in the above formula (1). Can be mentioned. Examples of the non-aromatic ring formed by R ⁴ and R ⁵ together with the adjacent carbon atom include the above-mentioned non-aromatic carbocycle and non-aromatic heterocycle.

Typical examples of the compound represented by the formula (1d) include 3-acetyloxy-2-oxo-1-oxaspiro [4.5] decane and 3-acetyloxy-2-oxo-1-oxaspiro. [4.4] Nonane, 3-acetyloxy-4-methyl-2-oxo-1-oxaspiro [4.5] decane, 3-acetyloxy-4-methoxycarbonyl-2-oxo-1-oxaspiro [4. 5]
Decane, 3-acetyloxy-3-methyl-2-oxo-1-oxaspiro [4.5] decane, 2-oxo-3
-Propionyloxy-1-oxaspiro [4.5] decane and 4-acetyloxydihydrospiro [furan-2 (5H), 2'-tricyclo [3.3.1.1] represented by the following formula (17). ^3,7 ] decane] -5-one and the like.

[Chemical formula 26]

Α-Substituted oxy-γ-represented by the formula (1d)
The butyrolactone derivative is, for example, the following α-hydroxy-γ-butyrolactone derivative and the following formula (5):

[Chemical 27] It can be produced by reacting an acyl halide derivative represented by the formula (wherein X ⁶ and Z are the same as above) in the presence of a base. As the base, the same bases as in the case of the compound of the above formula (1a) can be used.

The reaction is usually carried out in an organic solvent. As the organic solvent, the same solvent as in the case of the compound of the above formula (1a) can be used. The amount of the acyl halide derivative represented by the formula (5) and the base used is, for example, 0.8 to 5 relative to 1 mol of the α-hydroxy-γ-butyrolactone derivative corresponding to the compound of the formula (1d). It is about molar. The reaction temperature can be appropriately selected depending on the type of reaction components, but is usually in the range of about -10 ° C to 100 ° C.

After completion of the reaction, the reaction product can be separated and purified by a separating means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination thereof. In addition, α-hydroxy-corresponding to the compound of the formula (1d) used as a reaction raw material
The γ-butyrolactone derivative can be obtained by a known method, for example, W
It can be obtained by the method described in O00 / 35835 or a method analogous thereto.

[Compound represented by Formula (1e)] The above formula (1
In e), X ⁷ represents a saturated hydrocarbon group which may have a substituent. R ² , R ³ , R ⁴ and R ⁵ are the same or different and each represent a hydrogen atom, a hydrocarbon group which may have a substituent, or a substituted oxycarbonyl group. R ² , R ³ , R
^A plurality of R ⁴ and R ⁵ may combine to form a ring together with 1 to 3 carbon atoms constituting the γ-butyrolactone ring. However, R ⁴ and R ⁵ are groups other than hydrogen atom.

The saturated hydrocarbon group which may have a substituent in X ⁷ has a substituent among those described above as the hydrocarbon group which may have a substituent in X ^e . And a group corresponding to a saturated hydrocarbon group. As the saturated hydrocarbon group, for example, an alkyl group having about 1 to 20 (preferably 1 to 10) carbon atoms, a cycloalkyl having about 3 to 20 members (preferably 3 to 15 members, more preferably 5 to 8 members). Group, a bridged cyclic group such as an adamantyl group, a cycloalkyl-alkyl group (for example, a C _3-20 cycloalkyl-C _1-4 alkyl group, etc.) and the like. Examples of X ⁷ include C _1-10 alkyl group (especially C _1-5 alkyl group), C _3-15 cycloalkyl group, C _6-15 bridged cyclic group, C _3-15 cycloalkyl-C _{1 -4} alkyl group, C _1-10 haloalkyl group (especially C _1-5 haloalkyl group) and the like are preferable.

A hydrocarbon group which may have a substituent for R ² , R ³ , R ⁴ and R ⁵ , a substituted oxycarbonyl group,
And preferred groups among them are those represented by the above formula (1)
"The hydrocarbon group which may have a substituent" exemplified as the substituent which the γ-butyrolactone ring in may have.
And groups similar to the “substituted oxycarbonyl group”. In addition, a plurality of R ² , R ³ , R ⁴ and R ⁵ are combined to form γ
-A ring formed together with 1 to 3 carbon atoms constituting a butyrolactone ring, and a preferred ring among them is γ-butyrolactone ring in which a plurality of substituents on the γ-butyrolactone ring are bonded to each other. 1-constituting the butyrolactone ring
The same rings as those exemplified as the ring formed with 3 carbon atoms can be mentioned.

As typical examples of the compound represented by the formula (1e), α-acetyloxy-γ, γ-dimethyl-γ-butyrolactone, α-acetyloxy-β, γ, γ-trimethyl-γ-butyrolactone , Α-acetyloxy-γ
-Ethyl-γ-methyl-γ-butyrolactone, γ, γ-
Examples thereof include dimethyl-α-propionyloxy-γ-butyrolactone and γ, γ-dimethyl-α-butyryloxy-γ-butyrolactone.

Α-Substituted oxy-γ-represented by the formula (1e)
The butyrolactone derivative is, for example, a compound represented by the following formula (6) with a corresponding α-hydroxy-γ-butyrolactone derivative.

[Chemical 28] It can be produced by reacting an acyl halide derivative represented by the formula (wherein X ⁷ and Z are the same as above) in the presence of a base. As the base, the same bases as in the case of the compound of the above formula (1a) can be used.

The reaction is usually carried out in an organic solvent. As the organic solvent, the same solvent as in the case of the compound of the above formula (1a) can be used. The amounts of the acyl halide derivative represented by the formula (6) and the base are, for example, 0.8 to 5 relative to 1 mol of the α-hydroxy-γ-butyrolactone derivative corresponding to the compound of the formula (1e). It is about molar. The reaction temperature can be appropriately selected depending on the type of reaction components, but is usually in the range of about -10 ° C to 100 ° C.

After completion of the reaction, the reaction product can be separated and purified by a separating means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination thereof. In addition, α-hydroxy-corresponding to the compound of the formula (1e) used as a reaction raw material
The γ-butyrolactone derivative can be obtained by a known method, for example, W
It can be obtained by the method described in O00 / 35835 or a method analogous thereto.

[Compound represented by Formula (1f)] The above formula (1
In f), X ⁸ represents a hydrocarbon group which may have a substituent. R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different and represent a hydrogen atom, an optionally substituted hydrocarbon group or a substituted oxycarbonyl group. R ¹ , R ² , R
^A plurality of ³ , R ⁴ and R ⁵ may combine to form a ring together with 1 to 3 carbon atoms constituting the γ-butyrolactone ring. However, R ² is a substituted oxycarbonyl group, and R ⁴ and R ⁵ are groups other than hydrogen atom.

Examples of the hydrocarbon group which may have a substituent in X ⁸ include the same groups as those described above as the hydrocarbon group which may have a substituent in X ^e . The X ^8, in particular, C _1-10 alkyl (especially C _1-5 alkyl group), C _{2- 10} alkenyl groups, C
_2-10 alkynyl group, C _3-15 cycloalkyl group, C _6-15 bridged cyclic group, substituent (for example, halogen atom, C _1-4 alkoxy group, C _1-4 alkoxycarbonyl group, nitro group, C _1-4 alkyl group, C _1-4 haloalkyl group) optionally C _6-10 aryl group optionally having, C _3-15 cycloalkyl -C _1-4 alkyl group, C _{7 -14} aralkyl group, A C _1-10 haloalkyl group (particularly a C _1-5 haloalkyl group) and the like are preferable.

The hydrocarbon group which may have a substituent in R ¹ , R ² , R ³ , R ⁴ and R ⁵ , the substituted oxycarbonyl group, and a preferable group thereof are those represented by the above formula (1 The same groups as the "hydrocarbon group which may have a substituent" and the "substituted oxycarbonyl group" which are exemplified as the substituent which the γ-butyrolactone ring in () may have. Further, as a ring formed by combining a plurality of R ¹ , R ² , R ³ , R ⁴ and R ⁵ together with 1 to 3 carbon atoms constituting a γ-butyrolactone ring, and preferable rings among them Is a ring similar to the ring exemplified as the ring formed with 1 to 3 carbon atoms constituting the γ-butyrolactone ring by bonding a plurality of substituents on the γ-butyrolactone ring in the above formula (1). Can be mentioned.

As a typical example of the compound represented by the formula (1f), α-acetyloxy-β-methoxycarbonyl-
γ, γ-dimethyl-γ-butyrolactone, α-acetyloxy-β-ethoxycarbonyl-γ, γ-dimethyl-
γ-butyrolactone, α-acetyloxy-β-methoxycarbonyl-α, γ, γ-trimethyl-γ-butyrolactone, β-methoxycarbonyl-γ, γ-dimethyl-
Examples include α-propionyloxy-γ-butyrolactone.

Α-Substituted oxy-γ-represented by the formula (1f)
The butyrolactone derivative is, for example, a compound represented by the following formula (7) with the corresponding α-hydroxy-γ-butyrolactone derivative.

[Chemical 29] It can be produced by reacting with an acyl halide derivative represented by the formula (wherein X ⁸ and Z are the same as above) in the presence of a base. As the base, the same bases as in the case of the compound of the above formula (1a) can be used.

The reaction is usually carried out in an organic solvent. As the organic solvent, the same solvent as in the case of the compound of the above formula (1a) can be used. The amount of the acyl halide derivative represented by the formula (7) and the base to be used is, for example, 0.8 to 5 relative to 1 mol of the α-hydroxy-γ-butyrolactone derivative corresponding to the compound of the formula (1f). It is about molar. The reaction temperature can be appropriately selected depending on the type of reaction components, but is usually in the range of about -10 ° C to 100 ° C.

After the completion of the reaction, the reaction product can be separated and purified by a separating means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography or a combination thereof. In addition, α-hydroxy-corresponding to the compound of the formula (1f) used as a reaction raw material
The γ-butyrolactone derivative can be obtained by a known method, for example, W
It can be obtained by the method described in O00 / 35835 or a method analogous thereto.

[Compound represented by Formula (1g)] The above formula (1
In g), X ⁹ represents a hydrocarbon group which may have a substituent. R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different and represent a hydrogen atom, an optionally substituted hydrocarbon group or a substituted oxycarbonyl group. R ¹ , R ² , R
^A plurality of ³ , R ⁴ and R ⁵ may combine to form a ring together with 1 to 3 carbon atoms constituting the γ-butyrolactone ring. However, R ¹ , R ⁴ and R ⁵ are groups other than hydrogen atom.

Examples of the hydrocarbon group which may have a substituent in X ⁹ include the same groups as those described above as the hydrocarbon group which may have a substituent in X ^f . The X ^9, in particular, C _1-10 alkyl (especially C _1-5 alkyl group), C _{2- 10} alkenyl groups, C
_2-10 alkynyl group, C _3-15 cycloalkyl group, C _6-15 bridged cyclic group, C _6-10 aryl group, C _3-15 cycloalkyl-C _1-4 alkyl group, C _7-14 aralkyl A group and the like are preferable.

The hydrocarbon group which may have a substituent in R ¹ , R ² , R ³ , R ⁴ and R ⁵ , the substituted oxycarbonyl group, and preferable groups among them are those represented by the above formula (1 The same groups as the "hydrocarbon group which may have a substituent" and the "substituted oxycarbonyl group" which are exemplified as the substituent which the γ-butyrolactone ring in () may have. Further, as a ring formed by combining a plurality of R ¹ , R ² , R ³ , R ⁴ and R ⁵ together with 1 to 3 carbon atoms constituting a γ-butyrolactone ring, and preferable rings among them Is a ring similar to the ring exemplified as the ring formed with 1 to 3 carbon atoms constituting the γ-butyrolactone ring by bonding a plurality of substituents on the γ-butyrolactone ring in the above formula (1). Can be mentioned.

As typical examples of the compound represented by the formula (1g), α-methoxy-α, γ, γ-trimethyl-γ-butyrolactone, α-methoxy-α, β, γ, γ-tetramethyl- γ-butyrolactone, β-trifluoromethyl-α-methoxy-α, γ, γ-trimethyl-γ-butyrolactone, α-methoxy-α, γ, γ-trimethyl-β
-Phenyl-γ-butyrolactone, α-methoxy-β-
Methoxycarbonyl-α, γ, γ-trimethyl-γ-butyrolactone, 3-methoxy-3-methyl-2-oxo-1-oxaspiro [4.5] decane, α-ethoxy-
α, γ, γ-trimethyl-γ-butyrolactone, α,
γ, γ-trimethyl-α-propoxy-γ-butyrolactone and the like can be mentioned.

Α-Substituted oxy-γ-represented by the formula (1g)
The butyrolactone derivative is, for example, a compound represented by the following formula (8) with a corresponding α-hydroxy-γ-butyrolactone derivative.

[Chemical 30] It can be produced by reacting a halogenated hydrocarbon compound represented by the formula (wherein X ⁹ and Z are the same as above) in the presence of a base. As the base, the same bases as in the case of the compound of the above formula (1a) can be used.

The reaction is usually carried out in an organic solvent. As the organic solvent, the same solvent as in the case of the compound of the above formula (1a) can be used. The amount of the halogenated hydrocarbon compound represented by the formula (8) and the base to be used is, for example, 0.8 with respect to 1 mol of the α-hydroxy-γ-butyrolactone derivative corresponding to the compound of the formula (1g). -5 mol, preferably 0.8-2 mol. The reaction temperature can be appropriately selected depending on the type of reaction components, but is usually -10 ° C to 100 ° C.
It is a range of degrees.

After the completion of the reaction, the reaction product can be separated and purified by a separating means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography or a combination thereof. In addition, α-hydroxy-corresponding to the compound of the formula (1g) used as a reaction raw material
The γ-butyrolactone derivative can be obtained by a known method, for example, W
It can be obtained by the method described in O00 / 35835 or a method analogous thereto.

[Electrolytic Solution] The electrolytic solution of the present invention contains the α-substituted oxy-γ-butyrolactone derivative represented by the above formula (1) as a solvent. The α-substituted oxy-γ-butyrolactone derivative represented by the formula (1) may be a solid in some cases, but in that case, it will be treated as a “solvent” for convenience. The α-substituted oxy-γ-butyrolactone derivative represented by the formula (1) is used alone or in combination of two or more.

The solvent of the electrolytic solution may be composed of only the α-substituted oxy-γ-butyrolactone derivative represented by the above formula (1), but normally, the α represented by the above formula (1) is used.
It is composed of a combination of a -substituted oxy-γ-butyrolactone derivative and another solvent. The other solvent may be any solvent that can be used as a solvent for the electrolytic solution,
A known non-aqueous solvent for electrolytic solution can be used. As a typical example of such a solvent, for example, ethylene carbonate,
Cyclic carbonic acid esters such as propylene carbonate, butylene carbonate, vinylene carbonate; γ-butyrolactone, α-methyl-γ-butyrolactone, α-propyl-γ-butyrolactone, α-pentyl-γ-butyrolactone, α-halo-γ-butyrolactone, β-methyl-γ-butyrolactone, α-halo-β-methyl-γ-butyrolactone, α-acetyl-γ-butyrolactone, δ
-Cyclic carboxylic acid esters such as valerolactone; dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, isopropyl methyl carbonate, ethyl propyl carbonate, diisopropyl carbonate, dibutyl carbonate, 2,2,2-trifluoroethyl-methyl carbonate , 2,2,2-trichloroethyl-methyl carbonate, 3,3,3-trifluoropropyl-methyl carbonate, etc .; chain carbonic acid esters; chain carbonic acid, such as acetic acid alkyl ester, propionic acid alkyl ester, malonic acid dialkyl ester, etc. Acid esters; cyclic ethers such as tetrahydrofuran and 1,3-dioxolane;
Chain ethers such as dimethoxyethane and 1,3-dimethoxypropane; 5,5-dimethyl-dihydro-2,3-
Ketolactones such as furanone; 5,5-dimethyl-2-
Cyclic keto acetals such as methoxytetrahydrofuran-3-one; cyclic hydroxy acetals such as 5,5-dimethyl-3-methyl-tetrahydrofuran-2,3-diol; 4,4-dimethyl-2-hydroxy-γ-butyrolactone and the like Hydroxy lactone; cyclic borate ester such as trimethylene borate; 2-hydroxy-2
Examples thereof include hydroxyketoesters such as -methyl-1,4-dioxo-methyl valerate. These solvents may be used alone or in combination of two or more. Among these, a cyclic carbonate such as ethylene carbonate or propylene carbonate; or a mixture of the cyclic carbonate and another solvent (for example, a chain carbonate such as dimethyl carbonate) is particularly preferable.

Α-Substituted oxy-γ-represented by the formula (1)
When a butyrolactone derivative and another solvent are used in combination, the ratio is, for example, the former: the latter (volume ratio).
= 0.1: 99.9 to 90:10, preferably the former:
The latter (capacity ratio) = 1: 99 to 50:50, and more preferably the former: latter (capacity ratio) = 2: 98 to 30:70. The “volume” when these components are solid at room temperature means the volume in a state of being heated and melted.

The electrolyte constituting the electrolytic solution is not particularly limited as long as it functions as an electrolyte, and any known electrolyte can be used. Typical electrolytes include, for example, LiClO ₄ , LiBF ₄ , LiPF ₆ , LiAlC.
_{l 4, LiSbF 6, LiAsF 6} , LiB 10 Cl 10, L
Inorganic lithium salts such as iCl, LiBr, LiI, and chloroborane lithium; LiSCN, Li (CF ₃ SO ₃ ),
Li (C ₂ F ₅ SO ₃ ), Li (C ₃ F ₇ SO ₃ ), Li (C
₄ F ₉ SO ₃ ), Li (C ₅ F ₁₁ SO ₃ ), Li (C ₆ F ₁₃ S
_{O 3), Li (C 7} F 15 SO 3), Li (CF 3 CO 2),
Li (CF ₃ SO ₂ ) ₂ , LiB (C ₆ H ₅ ) ₄ , LiN (C
_{F 3 SO 2) 2, LiN} (C 2 F 5 SO 2) 2, LiN (CF 3
_{SO 2) (C 4 F 9} SO 2), LiC (CF 3 SO 2) 3, bis (1,2-benzene diolate (2 -) - O, O ')
Lithium borate, bis (2,3-naphthalenedioleate (2-)-O, O ′) lithium borate, bis (2,2 ′)
Examples include organic lithium salts such as lithium biphenyldiolate (2-)-O, O ') and lithium bis (5-fluoro-2-oleate-1-benzenesulfone-O, O') borate. These electrolytes alone or
A combination of two or more species can be used.

The concentration of the electrolyte can be appropriately selected depending on, for example, the amount of the positive electrode material or the negative electrode material of the battery, the size of the battery, and the like, but is generally about 0.2 to 2 mol / l (M), preferably 0.1. It is about 5 to 1.5 mol / l (M).

Other compounds may be added to the electrolytic solution in order to improve discharge and charge / discharge characteristics. Examples of such compounds include phosphorus compounds such as triethylphosphite and hexaphosphoric acid triamide; amines such as triethanolamine and ethylenediamine; nitrogen-containing aromatic heterocyclic compounds such as pyridine; nitro compounds such as nitrobenzene; Crown ethers; quaternary ammonium salts and the like are included.

[Non-Aqueous Electrochemical Device] The non-aqueous electrochemical device of the present invention comprises the above electrolytic solution. Non-aqueous electrochemical devices include, for example, batteries such as non-aqueous electrolyte secondary batteries, capacitors for electric double layers, and the like. A non-aqueous electrochemical device is generally composed of at least two electrodes, a separator interposed between the two electrodes, and the electrolyte solution. In a non-aqueous electrolyte secondary battery (such as a lithium secondary battery), the two electrodes are a positive electrode and a negative electrode.

For the positive electrode and the negative electrode, for example, a positive electrode active material capable of electrochemically and reversibly occluding / releasing lithium ions or a negative electrode material and a mixture layer containing a conductive agent, a binder and the like on the surface of the current collector. It can be prepared by coating.

As the negative electrode material (negative electrode active material), for example, metallic lithium, lithium alloys, materials capable of inserting and extracting lithium, for example, carbon materials (for example, pyrolytic carbons, cokes, graphites, polymer fired bodies) , Carbon fibers, activated carbon, etc., conductive polymers, lithium-containing transition metal oxides or sulfides, tin compounds, lead compounds, bismuth compounds, silicon compounds, intermetallic compounds, lithium nitrogen compounds, and the like. Not limited.

Examples of the conductive agent for the negative electrode include graphite such as natural graphite and artificial graphite; carbon black such as acetylene black and furnace black; conductive fibers such as carbon fiber and metal fiber; fluorocarbon, copper, and the like.
Metal powders such as nickel; organic conductive materials such as polyphenylene derivatives and the like. These alone or 2
It can be used in combination of two or more species. The conductive agent does not necessarily have to be added.

As the binder for the negative electrode, a thermoplastic resin or a thermosetting resin can be used. Typical binders include, for example, olefin resins such as polyethylene and polypropylene; polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, ethylene- Tetrafluoroethylene copolymer, propylene-tetrafluoroethylene copolymer, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-chlorotrifluoroethylene copolymer, vinylidene fluoride-perfluoromethyl Vinyl ether-tetrafluoroethylene copolymer, vinylidene fluoride-pentafluoropropylene copolymer, polychlorotrifluoroethylene, ethylene-chlorotrifluoroethylene copolymer, etc. Fluorine-based resin; styrene-butadiene rubber; ethylene-acrylic acid copolymer or its sodium ion crosslinked product, ethylene-methacrylic acid copolymer or its sodium ion crosslinked product, ethylene-methyl acrylate copolymer, ethylene-methacryl A copolymer of ethylene and an acrylic monomer such as a methyl acid copolymer is included. These binders can be used alone or in combination of two or more kinds.

The negative electrode current collector may be any stable conductor that does not undergo a chemical change during use, and examples thereof include stainless steel, nickel, copper, copper alloys, titanium, carbon and conductive resins. To be The negative electrode current collector may be subjected to an appropriate surface treatment. The shape of the negative electrode current collector is not particularly limited, and may be a foil shape, a film shape, a net shape, a porous body, a foam body, or the like. The thickness of the negative electrode current collector is, for example, about 0.5 to 1000 μm.

Examples of the positive electrode material (positive electrode active material) include LiCoO ₂ , LiNiO ₂ , LiMnO ₂ and LiM.
Lithium-containing composite oxide such as n ₂ O ₄ ; TiO ₂ , Mn
Transition metal chalcogenides such as O ₂ , MoO ₃ , V ₂ O ₅ , TiS ₂ , and MoS ₂ ; organic conductive substances and the like can be used, but not limited thereto.

As the positive electrode conductive agent and the positive electrode binder, the same ones as exemplified as the negative electrode conductive agent and the negative electrode binder can be used, respectively. The positive electrode current collector may be any stable conductor that does not chemically change during use, and examples thereof include stainless steel, aluminum, aluminum alloys, titanium, carbon, and conductive resins. The current collector may be subjected to an appropriate surface treatment.
The shape of the negative electrode current collector is not particularly limited, and may be a foil shape, a film shape, a net shape, a porous body, a foam body, or the like. The thickness of the negative electrode current collector is, for example, 0.5 to 1
It is about 000 μm.

In addition to the electrode mixture, various additives such as a filler, a dispersant, an ion conductive agent and a pressure enhancer may be added.

As the separator, an insulating microporous thin film having ion permeability is used. As the separator, for example, a sheet made of olefin resin such as polyethylene or polypropylene, or glass fiber,
Examples include non-woven fabrics and woven fabrics. The pore size of the separator is
For example, it is about 0.005 to 2 microns. The thickness of the separator is, for example, about 5 to 500 microns.

The shape of the battery is not particularly limited and may be any of coin type, button type, sheet type, laminated type, cylindrical type, flat type, prismatic type and the like. The configuration of the non-aqueous electrochemical device is not limited to the above, and various configurations can be adopted as long as the electrolytic solution of the present invention is included.

The non-aqueous electrochemical device of the present invention includes a portable information terminal, a portable electronic device, a hybrid electric vehicle, an electric vehicle, a motorcycle, an electric wheelchair, an industrial power storage system, a domestic power storage system, a solar system, etc. However, the present invention is not limited to these.

According to the electrolytic solution of the present invention, high charge / discharge efficiency and / or high capacity retention rate can be obtained when used in a non-aqueous electrolytic solution electrochemical device. Since the non-aqueous electrolyte electrochemical device of the present invention comprises the above-mentioned electrolyte, it exhibits high charge / discharge efficiency and / or high capacity retention rate. Further, according to the present invention, a novel α-substituted oxy-γ-butyrolactone derivative useful as a component (solvent or additive) of an electrolytic solution is provided.

[0117]

The present invention will be described in more detail based on the following examples, but the invention is not intended to be limited by these examples.

Production Example 1 While a mixture of 25 mmol of α-hydroxy-γ, γ-dimethyl-γ-butyrolactone, 50 ml of toluene and 75 mmol of pyridine was stirred at 0 ° C., 75 mmol of methyl chloroformate was added, and then the solution was added. The mixture was stirred at 50 ° C for 1 hour. The reaction mixture was washed with 50 ml of water, concentrated under reduced pressure, and the concentrate was subjected to silica gel column chromatography to obtain α-methoxycarbonyloxy-γ, γ-dimethyl-γ-butyrolactone represented by the following formula (9). Was obtained in a yield of 49%. [Α-methoxycarbonyloxy-γ, γ-dimethyl-
Spectral data of γ-butyrolactone] ¹ H-NMR (CDCl ₃ ) δ: 1.46 (s, 3H),
1.53 (s, 3H), 2.16-2.20 (dd, 1
H), 2.58-2.62 (dd, 1H), 3.85.
(S, 3H), 5.46-5.50 (m, 1H) ¹³ C-NMR (CDCl ₃ ) δ: 27.8, 28.9,
40.6, 55.5, 72.2, 82.1, 154.
7, 171.2 MS m / e 189 (M + H), 113

[Chemical 31]

Production Example 2 A mixture of 25 mmol of α-hydroxy-γ, γ-dimethyl-γ-butyrolactone, 50 ml of toluene and 38 mmol of N, N-diisopropylethylamine was stirred at 0 ° C. while 38 mmol of chloromethyl methyl ether was added. After the addition, the mixture was stirred at 45 ° C for 5 hours. Reaction mixture with water 5
After washing with 0 ml, the mixture was concentrated under reduced pressure, and the concentrate was subjected to silica gel column chromatography to obtain α-methoxymethoxy-γ, γ-dimethyl-γ-butyrolactone represented by the following formula (10) with a yield of 68%. Obtained. [Spectral data of α-methoxymethoxy-γ, γ-dimethyl-γ-butyrolactone] ¹ H-NMR (CDCl ₃ ) δ: 1.41 (s, 3H),
1.51 (s, 3H), 2.04-2.10 (m, 1
H), 2.43-2.49 (m, 1H), 3.42.
(S, 3H), 4.54-4.61 (m, 1H), 4.
70-4.71 (d, 1H), 4.96-4.97.
(D, 1H) ¹³ C-NMR (CDCl ₃ ) δ: 27.8, 29.0,
41.9, 55.8, 71.9, 81.9, 96.0,
174.4 MS m / e 175 (M + H), 143

[Chemical 32]

Production Example 3 Similar to Production Example 2 except that 25 mmol of α-hydroxy-α, γ, γ-trimethyl-γ-butyrolactone was used in place of α-hydroxy-γ, γ-dimethyl-γ-butyrolactone. Was performed, and α-methoxymethoxy-α, γ, γ-trimethyl-represented by the following formula (11) was obtained.
γ-butyrolactone was obtained with a yield of 43%. [Α-methoxymethoxy-α, γ, γ-trimethyl-γ
-Spectral data of butyrolactone] ¹ H-NMR (CDCl ₃ ) δ: 1.45 (s, 3H),
1.53 (s, 3H), 1.54 (s, 3H), 2.0
3-2.05 (d, 1H), 2.45-2.48 (d,
1H), 3.39 (s, 3H), 4.70-4.72.
(D, 1H), 4.95-4.97 (d, 1H) ¹³ C-NMR (CDCl ₃ ) δ: 22.8, 28.9,
29.5, 48.2, 56.0, 78.9, 81.9,
92.4, 175.6 MS m / e 189 (M + H), 157

[Chemical 33]

Production Example 4 β-Trifluoromethyl-α-hydroxy-γ, γ-dimethyl-γ-butyrolactone 25 mmol, toluene 5
While stirring a mixture of 0 ml and pyridine (33 mmol) at room temperature, acetyl chloride (33 mmol) was added, and the mixture was stirred for 1 hour. The reaction solution was washed with 50 ml of water, concentrated under reduced pressure, and the concentrate was subjected to silica gel column chromatography to obtain α-acetyloxy-β-trifluoromethyl-γ, γ-dimethyl represented by the following formula (12). -Γ
-Butyrolactone was obtained with a yield of 52%. [Α-acetyloxy-β-trifluoromethyl-γ,
Spectra of γ-dimethyl-γ-butyrolactone] MS m / e 241 (M + H), 181

[Chemical 34]

Production Example 5 Instead of β-trifluoromethyl-α-hydroxy-γ, γ-dimethyl-γ-butyrolactone, α-hydroxy-γ- (3,3,3-trifluoropropyl) -γ-butyrolactone was used. The same operation as in Preparation Example 4 was carried out except that 25 mmol was used, and α-represented by the following formula (13) was used.
Acetyloxy-γ- (3,3,3-trifluoropropyl) -γ-butyrolactone was obtained with a yield of 50%. [Spectral data of α-acetyloxy-γ- (3,3,3-trifluoropropyl) -γ-butyrolactone] MS m / e 241 (M + H), 181

[Chemical 35]

Production Example 6 25 mmol of α-hydroxy-γ, γ-dimethyl-β-phenyl-γ-butyrolactone was used in place of β-trifluoromethyl-α-hydroxy-γ, γ-dimethyl-γ-butyrolactone. The same operation as in Production Example 4 was carried out except that the above was carried out, and α-acetyloxy-γ, γ-dimethyl-β-phenyl-γ-butyrolactone represented by the following formula (14) was obtained in a yield of 48%. . [Spectral data of α-acetyloxy-γ, γ-dimethyl-β-phenyl-γ-butyrolactone] MS m / e 249 (M + H), 189

[Chemical 36]

Production Example 7 Instead of β-trifluoromethyl-α-hydroxy-γ, γ-dimethyl-γ-butyrolactone, 3-hydroxy-2-oxo-1-oxaspiro [4.5] decane 25 was used.
The same operation as in Production Example 4 was carried out except that mmol was used, whereby 3-acetyloxy- represented by the following formula (15) was used.
2-Oxo-1-oxaspiro [4.5] decane was obtained with a yield of 56%. [Spectral data of [3-acetyloxy-2-oxo-1-oxaspiro [4.5] decane] MS m / e 213 (M + H), 153

[Chemical 37]

Production Example 8 Instead of β-trifluoromethyl-α-hydroxy-γ, γ-dimethyl-γ-butyrolactone, the following formula (16) was used.

[Chemical 38] Dihydro 4-hydroxyspiro [furan-2 represented by
Preparation Example 4 except that 25 mmol of (5H), 2′-tricyclo [3.3.1.1 ^3,7 ] decane] -5-one is used.
When a similar operation to that described above was performed, 4-acetyloxydihydrospiro [furan-2 (5
H), 2'tricyclo [3.3.1.1 ^{3, 7]} decan] -5-one was obtained in 48% yield. [4-acetyloxydihydrospiro [furan-2 (5
H), 2'tricyclo [3.3.1.1 ^{3, 7]} decane] -5 spectral data on] MS m / e 265 (M + H), 205

[Chemical Formula 39]

Preparation Example 9 Preparation was carried out except that 25 mmol of α-hydroxy-γ, γ-dimethyl-γ-butyrolactone was used instead of β-trifluoromethyl-α-hydroxy-γ, γ-dimethyl-γ-butyrolactone. When the same operation as in Example 4 was performed,
Α-acetyloxy-γ, γ-represented by the following formula (18)
Dimethyl-γ-butyrolactone was obtained with a yield of 82%. [Alpha-acetyloxy-gamma, .gamma.-dimethyl -γ- butyrolactone spectral _{^{data] 1 H-NMR (CDC1 3}} ) δ: 1.45 (s, 3H),
1.53 (s, 3H), 2.04-2.10 (m, 1
H), 2.16 (s, 3H), 2.57-2.63.
(M, 1H), 5.55-5.60 (dd, 1H) ¹³ C-NMR (CDCl ₃ ) δ: 20.6, 27.8,
29.0, 41.0, 69.2, 82.2, 169.
7, 172.1 MS m / e 173 (M + H), 113

[Chemical 40]

Production Example 10 25 mmol of α-hydroxy-β, γ, γ-trimethyl-γ-butyrolactone was used instead of β-trifluoromethyl-α-hydroxy-γ, γ-dimethyl-γ-butyrolactone. When the same operation as in Production Example 4 was performed, α-acetyloxy- represented by the following formula (19) was obtained.
Yield 6 of β, γ, γ-trimethyl-γ-butyrolactone
Obtained at 1%. [Α-acetyloxy-β, γ, γ-trimethyl-γ-
Butyrolactone Spectral Data] MS m / e 187 (M + H), 127

[Chemical 41]

Production Example 11 The same operation as in Production Example 4 was carried out except that 33 mmol of propanoyl chloride was used instead of acetyl chloride.
Γ, γ-Dimethyl-α-propanoyloxy-γ-butyrolactone represented by the following formula (20) was obtained at a yield of 62%. [Spectral data of γ, γ-dimethyl-α-propanoyloxy-γ-butyrolactone] MS m / e 187 (M + H), 113

[Chemical 42]

Production Example 12 In place of β-trifluoromethyl-α-hydroxy-γ, γ-dimethyl-γ-butyrolactone, γ-ethyl-α
The same operation as in Production Example 4 was carried out except that 25 mmol of -hydroxy-γ-methyl-γ-butyrolactone was used, and α-acetyloxy-γ represented by the following formula (21) was obtained.
Yield 62-ethyl-γ-methyl-γ-butyrolactone
Earned in%. [Α-acetyloxy-γ-ethyl-γ-methyl-γ-
Butyrolactone Spectral Data] MS m / e 187 (M + H), 127

[Chemical 43]

Production Example 13 Production Example 4 except that 25 mmol of α-hydroxy-γ-propyl-γ-butyrolactone was used in place of β-trifluoromethyl-α-hydroxy-γ, γ-dimethyl-γ-butyrolactone. When the same operation as in (1) was performed, α-acetyloxy-γ-n-propyl-γ-butyrolactone represented by the following formula (22) was obtained with a yield of 58%. [Spectral data of α-acetyloxy-γ-n-propyl-γ-butyrolactone] MS m / e 187 (M + H), 127

[Chemical 44]

Preparation Example 14 In place of β-trifluoromethyl-α-hydroxy-γ, γ-dimethyl-γ-butyrolactone, 25 mmol of α-hydroxy-α, γ, γ-trimethyl-γ-butyrolactone was used. Was subjected to the same operations as in Production Example 4 to obtain α-acetyloxy-expressed by the following formula (23).
Yield 5 of α, γ, γ-trimethyl-γ-butyrolactone
Obtained at 6%. [Α-Acetyloxy-α, γ, γ-trimethyl-γ-
Butyrolactone spectrum data] ¹ H-NMR (CDCl ₃ ) δ: 1.46 (s, 3H),
1.56 (s, 3H), 1.63 (s, 3H), 2.0
9 (s, 3H), 2.17-2.20 (d, 1H),
2.55-2.58 (d, 1H) ¹³ C-NMR (CDCl ₃ ) δ: 21.0, 25.3
29.3, 29.5, 45.9, 78.9, 81.0,
169.8, 174.6 MS m / e 187 (M + H), 127

[Chemical formula 45]

Production Example 15 25 mmol of α-hydroxy-β-methoxycarbonyl-γ, γ-dimethyl-γ-butyrolactone was used in place of β-trifluoromethyl-α-hydroxy-γ, γ-dimethyl-γ-butyrolactone. The same operation as in Production Example 4 was carried out except that it was used, and α- represented by the following formula (24)
Acetyloxy-β-methoxycarbonyl-γ, γ-dimethyl-γ-butyrolactone was obtained with a yield of 40%. [Α-acetyloxy-β-methoxycarbonyl-γ,
Spectra of γ-dimethyl-γ-butyrolactone] MS m / e 231 (M + H), 171

[Chemical formula 46]

Production Example 16 While a mixture of 50 ml of tetrahydrofuran and 25 mmol of lithium diisopropylamide was stirred at 0 ° C., 25 mmol of α-hydroxy-α, γ, γ-trimethyl-γ-butyrolactone was added thereto and stirred for 1 hour. . Thereafter, 30 mmol of methyl iodide was added, and the solution was stirred at 50 ° C. for 1 hour. The reaction mixture was washed with 50 ml of water, concentrated under reduced pressure, and the concentrate was subjected to silica gel column chromatography to obtain α-methoxy-α, γ, γ-trimethyl-γ-butyrolactone represented by the following formula (25). Was obtained in a yield of 10%. [Spectral data of α-methoxy-α, γ, γ-trimethyl-γ-butyrolactone] MS m / e 159 (M + H)

[Chemical 47]

Production Example 17 A mixture of 10 mmol of 1,1-carbonyldiimidazole and 4 ml of tetrahydrofuran was stirred at room temperature under a nitrogen atmosphere while 22 mmol of α-hydroxy-γ, γ-dimethyl-γ-butyrolactone was added thereto. added. The reaction mixture was stirred with heating under reflux for 2 hours. The reaction mixture was concentrated under reduced pressure, and the concentrate was subjected to column chromatography to give bis (γ, γ- represented by the following formula (32).
Dimethyl-γ-butyrolactone-α-yl) carbonate was obtained with a yield of 48%. [Bis (γ, γ-dimethyl-γ-butyrolactone-α-
Yield) carbonate spectral data] ¹ H-NMR (CDCl ₃ ) δ: 1.47 (s, 6H),
1.54 (s, 6H), 2.21 (dd, 2H), 2.
63 (dd, 2H), 5.56 (t, 2H) ¹³ C-NMR (CDCl ₃ ) δ: 27.8, 29.0,
40.5, 72.8, 82.3, 153.2, 170.
7 MS m / e 287 (M + H), 201, 175, 1
Thirteen

[Chemical 48]

Production Example 18 A mixture of 10 mmol of α-hydroxy-γ, γ-dimethyl-γ-butyrolactone, 20 ml of tetrahydrofuran and 15 mmol of pyridine was stirred at 0 ° C. under a nitrogen atmosphere while 15 mmol of allyl chloroformate was added thereto. After adding, the reaction mixture was stirred for 5 hours while heating under reflux.
Ethyl acetate (50 ml) was added to the reaction mixture, washed with water (50 ml), concentrated under reduced pressure, and the concentrate was subjected to column chromatography to obtain an α-represented by the following formula (33).
Allyloxycarbonyloxy-γ, γ-dimethyl-γ
-Butyrolactone was obtained with a yield of 32%. [Spectral data of α-allyloxycarbonyloxy-γ, γ-dimethyl-γ-butyrolactone] ¹ H-NMR (CDCl ₃ ) δ: 1.46 (s, 3H),
1.54 (s, 3H), 2.18 (dd, 1H), 2.
61 (dd, 1H), 4.69 (d, 2H), 5.30
(Dd, 1H), 5.40 (dd, 1H), 5.49
(T, 1H), 5.93 (m, 1H) ¹³ C-NMR (CDCl ₃ ) δ: 27.9, 29.0,
40.8, 69.4, 72.0, 82.0, 119.
3,130.5,153.9,171.1 MS m / e 215 (M + H), 113,41

[Chemical 49]

Production Example 19 Instead of allyl chloroformate, isobutyl chloroformate 15 was used.
The same operation as in Production Example 18 was carried out except that mmol was used, and α- (2-methylpropyloxycarbonyloxy) -γ, γ-dimethyl- represented by the following formula (34) was obtained.
γ-Butyrolactone was obtained with a yield of 52%. [Α- (2-methylpropyloxycarbonyloxy)
-Γ, γ-dimethyl-γ-butyrolactone spectral data] ¹ H-NMR (CDCl ₃ ) δ: 0.95 (d, 6H),
1.43 (s, 3H), 1.52 (s, 3H), 1.9
7 (m, 1H), 2.16 (dd, 1H), 2.58
(Dd, 1H), 3.97 (m, 1H), 5.45
(T, 1H) MS m / e 231 (M + H), 113

[Chemical 50]

Production Example 20 The same operation as in Production Example 18 was conducted except that 15 mmol of phenyl chloroformate was used in place of allyl chloroformate, and α-phenoxycarbonyloxy- represented by the following formula (35) was used. γ, γ-Dimethyl-γ-butyrolactone was obtained with a yield of 58%. [Spectral data of α-phenoxycarbonyloxy-γ, γ-dimethyl-γ-butyrolactone] ¹ H-NMR (CDCl ₃ ) δ: 1.47 (s, 3H),
1.56 (s, 3H), 2.26 (dd, 1H), 2.
66 (dd, 1H), 5.56 (t, 1H), 6.81
-7.43 (m, 5H) MS m / e 251 (M + H), 113

[Chemical 51]

Production Example 21 Phenyl chlorothioformate 1 was used in place of allyl chloroformate.
The same operation as in Production Example 18 was performed except that 5 mmol was used, and an α- (phenylthio) carbonyloxy-γ, γ-dimethyl-γ-butyrolactone represented by the following formula (36) was obtained in a yield of 35%. Got with. [Spectral data of α- (phenylthio) carbonyloxy-γ, γ-dimethyl-γ-butyrolactone] ¹ H-NMR (CDCl ₃ ) δ: 1.49 (s, 3H),
1.56 (s, 3H), 2.23 (dd, 1H), 2.
83 (dd, 1H), 6.08 (t, 1H), 7.12
-7.45 (m, 5H) ¹³ C-NMR (CDCl ₃ ) δ: 27.8, 29.0,
40.5, 77.0, 82.4, 121.4, 126.
8, 129.6, 153.4, 170.4, 194.2 MS m / e 267 (M + H), 113.

[Chemical 52]

Production Example 22 A mixture of 10 mmol of 1,1-carbonyldiimidazole and 10 ml of tetrahydrofuran was stirred at room temperature under a nitrogen atmosphere while adding 10 mmol of α-hydroxy-γ, γ-dimethyl-γ-butyrolactone. Cyclohexanone oxime 10 mmol, tetrahydrofuran 10
After adding ml, the reaction mixture was stirred for 2 hours while heating under reflux. The reaction mixture was concentrated under reduced pressure, and the concentrate was subjected to column chromatography to collect α-cyclohexylideneaminooxycarbonyloxy-γ, γ-dimethyl-γ-butyrolactone represented by the following formula (37). Obtained at a rate of 4%. [Spectral data of α-cyclohexylideneaminooxycarbonyloxy-γ, γ-dimethyl-γ-butyrolactone] MS m / e 269 (M + H), 113

[Chemical 53]

Example 1 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) to a concentration of 1 M, and then α-methoxycarbonyloxy-γ, obtained in Production Example 1, was dissolved in this solution. γ-Dimethyl-γ-butyrolactone was added to the solution so as to be 7% by volume to prepare an electrolytic solution.

Example 2 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) to a concentration of 1 M, and then α-methoxymethoxy-γ, γ obtained in Production Example 2 was added to this solution. -Dimethyl-γ-butyrolactone was added to the solution so as to be 7% by volume to prepare an electrolytic solution.

Example 3 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) to a concentration of 1 M, and then α-methoxymethoxy-γ represented by the following formula (26) was added to this solution. -Octyl-γ-butyrolactone was added to the solution so as to be 7% by volume to prepare an electrolytic solution.

[Chemical 54]

Example 4 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) to a concentration of 1 M, and the α-acetyloxy-β-tris obtained in Production Example 4 was dissolved in this solution. Fluoromethyl-γ, γ-dimethyl-γ-butyrolactone was added to the solution so as to be 7% by volume to prepare an electrolytic solution.

Example 5 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) to a concentration of 1 M, and α-acetyloxy-γ, γ obtained in Production Example 6 was dissolved in this solution. -Dimethyl-β-phenyl-γ-butyrolactone was added to the solution so as to be 7% by volume to prepare an electrolytic solution.

Example 6 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) to a concentration of 1 M, and the 3-acetyloxy-2-oxo obtained in Preparation Example 7 was added to this solution. -1-Oxaspiro [4.5] decane was added to the solution so as to be 7% by volume to prepare an electrolytic solution.

Example 7 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) to a concentration of 1 M, and α-acetyloxy-γ, γ obtained in Production Example 9 was dissolved in this solution. -Dimethyl-γ-butyrolactone was added to the solution so as to be 7% by volume to prepare an electrolytic solution.

Example 8 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) to a concentration of 1 M, and α-acetyloxy-α, γ obtained in Production Example 14 was dissolved in this solution. , Γ-Trimethyl-γ-butyrolactone was added to the solution so as to be 7% by volume to prepare an electrolytic solution.

Example 9 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) to a concentration of 1 M, and α-acetyloxy-γ represented by the following formula (27) was dissolved in this solution. -Methyl-γ-butyrolactone was added to the solution so as to be 7% by volume to prepare an electrolytic solution.

[Chemical 55]

Example 10 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) to a concentration of 1 M, and α-acryloyloxy-γ represented by the following formula (28) was dissolved in this solution. , Γ-Dimethyl-γ-butyrolactone was added to the solution so as to be 7% by volume to prepare an electrolytic solution.

[Chemical 56]

Example 11 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) to a concentration of 1 M, and the α-acetyloxy-β-methoxy obtained in Production Example 15 was dissolved in this solution. Carbonyl-γ, γ-dimethyl-γ-
Butyrolactone was added to the solution so as to be 7% by volume to prepare an electrolytic solution.

Example 12 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) so as to have a concentration of 1 M, and α-acetyloxy-β represented by the following formula (29) was dissolved in this solution. -Methoxycarbonyl-γ-octyl-γ-butyrolactone was added to the solution so as to be 7% by volume to prepare an electrolytic solution.

[Chemical 57]

Example 13 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) so as to have a concentration of 1 M, and then α-methoxy-obtained in Production Example 16 was added to this solution.
An electrolytic solution was prepared by adding α, γ, γ-trimethyl-γ-butyrolactone to the solution at 7% by volume.

Example 14 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) to a concentration of 1 M, and then α-methoxy-type represented by the following formula (30) was added to this solution.
γ-Methyl-γ-butyrolactone was added to the solution so as to be 7% by volume to prepare an electrolytic solution.

[Chemical 58]

Example 15 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) so as to have a concentration of 1 M, and the bis (γ, γ-dimethyl-containing compound obtained in Production Example 17 was dissolved in this solution. γ-Butyrolactone-α-yl) carbonate was added to the solution so as to be 7% by volume to prepare an electrolytic solution.

Example 16 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) to a concentration of 1 M, and α-allyloxycarbonyloxy-γ obtained in Production Example 18 was dissolved in this solution. , Γ-Dimethyl-γ-butyrolactone was added to the solution so as to be 7% by volume to prepare an electrolytic solution.

Example 17 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) to a concentration of 1 M, and the α- (2-methylpropyloxy group obtained in Production Example 19 was dissolved in this solution. Carbonyloxy) -γ, γ-dimethyl-γ-butyrolactone was added to the solution so as to be 7% by volume to prepare an electrolytic solution.

Example 18 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) to a concentration of 1 M, and then α-phenoxycarbonyloxy-γ, obtained in Production Example 20, was added to this solution. γ-Dimethyl-γ-butyrolactone was added to the solution so as to be 7% by volume to prepare an electrolytic solution.

Example 19 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) to a concentration of 1 M, and then α- (phenylthio) carbonyloxy-obtained in Production Example 21 was added to this solution. γ, γ-Dimethyl-γ-butyrolactone was added to the solution so as to be 7% by volume to prepare an electrolytic solution.

Example 20 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) to a concentration of 1 M, and the α-cyclohexylideneaminooxy compound obtained in Production Example 22 was dissolved in this solution. Carbonyloxy-γ, γ-dimethyl-γ-butyrolactone was added to the solution so as to be 7% by volume to prepare an electrolytic solution.

Example 21 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) so as to have a concentration of 1 M, and then the solution represented by the following formula (38) was used.

[Chemical 59] Α-acetyloxy-β, β-dimethyl-γ represented by
-Butyrolactone was added to the solution so as to be 7% by volume to prepare an electrolytic solution.

Example 22 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) so as to have a concentration of 1 M, and then this solution was added with the following formula (39).

[Chemical 60] 7% by volume of α-methoxycarbonyloxy-β, β-dimethyl-γ-butyrolactone represented by
And an electrolytic solution were prepared.

Comparative Example 1 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) to a concentration of 1 M to prepare an electrolytic solution.

Comparative Example 2 Lithium perchlorate (LiClO ₄ ) was dissolved in propylene carbonate (PC) to a concentration of 1 M, and then α-hydroxy-γ represented by the following formula (31) was added to this solution. γ-Dimethyl-γ-butyrolactone was added to the solution so as to be 7% by volume to prepare an electrolytic solution.

[Chemical formula 61]

Test Example 1 (Measurement of Charge / Discharge Efficiency) A mixed electrode made of natural graphite and polyvinylidene fluoride was prepared as an electrode, and this natural graphite electrode was used as a working electrode, lithium metal was used as a counter electrode and a reference electrode, and an electrolyte solution was used. As a glass beaker type triode cell, a glass beaker type cell was prepared by using the materials prepared in Examples 1 to 22 or Comparative Example 1 above. In order to improve the familiarity between the electrode and the electrolytic solution, the cell was left for 12 hours after being manufactured. In order to investigate the characteristics of the electrolytic solution with respect to the graphite negative electrode, a charge / discharge test was carried out at a rate of C / 24 using the above cell, and the charge / discharge efficiency in the first cycle was measured. The results are shown in Table 1. The charge / discharge efficiency is a value given by the following equation. Charge / discharge efficiency (%) = (discharge capacity / charge capacity) × 100 When the electrolytic solution of Comparative Example 1 was used, solvent decomposition occurred and charging could not be performed. Further, when the electrolytic solution of Example 10 was used, the performance was deteriorated when stored at high temperature.

[0165]

[Table 1]

Test Example 2 (Measurement of Capacity Retention Ratio) A mixed electrode made of natural graphite and polyvinylidene fluoride was prepared as an electrode, this natural graphite electrode was used as a working electrode, and lithium metal was used as a counter electrode and a reference electrode. As a glass beaker type triode cell, a glass beaker type triode cell was prepared by using the materials prepared in Examples 1, 2, 7 or Comparative Examples 1, 2. In order to improve the familiarity between the electrode and the electrolytic solution, the cell was left for 12 hours after being manufactured. In order to investigate the characteristics of the electrolytic solution with respect to the graphite negative electrode, a charge / discharge test was performed 10 cycles at a current density of C / 24 at 25 ° C. using the above-mentioned cell to measure the capacity retention rate. The results are shown in Table 2. The capacity retention rate is a value given by the following equation. Capacity retention rate (%) = (discharge capacity at 10th cycle / discharge capacity at 2nd cycle) × 100 When the electrolytic solutions of Comparative Examples 1 and 2 were used, solvent decomposition occurred and charging was not possible.

[0167]

[Table 2]

Test Example 3 (Measurement of Capacity Retention in Coin-Type Battery) A positive electrode was made of a mixture electrode made of lithium cobalt oxide and polyvinylidene fluoride, and a negative electrode was made of a mixture electrode made of natural graphite and polyvinylidene fluoride. The lithium cobalt oxide electrode as a positive electrode, the natural graphite electrode as a negative electrode, and the electrolyte prepared in Example 7 or Comparative Examples 1 and 2 using a polypropylene porous membrane as a separator, and a coin according to a conventional method. Type lithium secondary battery was produced. In order to improve the familiarity between the electrode and the electrolytic solution, the cell was left for 12 hours after being manufactured. In order to investigate the battery characteristics of the electrolytic solution, a charge / discharge test was performed at 25 ° C. at a current density of C / 24 for 10 cycles using the above-mentioned cell to measure the capacity retention rate. The results are shown in Table 3. The capacity retention rate is a value given by the following equation. Capacity retention rate (%) = (discharge capacity at 10th cycle / discharge capacity at 2nd cycle) × 100 When the electrolytic solutions of Comparative Examples 1 and 2 were used, solvent decomposition occurred and charging was not possible.

[0169]

[Table 3]

   ─────────────────────────────────────────────────── ─── Continued front page    F term (reference) 5H029 AJ05 AJ07 AK02 AK03 AK05                       AK16 AL01 AL02 AL04 AL06                       AL12 AL16 AM02 AM05 AM07                       HJ02

Claims (11)

[Claims] 1. The following formula (1): (In the formula, X represents an organic group which forms a carbonate, thiocarbonate, acetal, ester or ether together with an adjacent oxygen atom. In the formula, the γ-butyrolactone ring may have a substituent, May form a ring with 1 to 3 carbon atoms forming a γ-butyrolactone ring by bonding, provided that when X is an organic group which forms an ether with an adjacent oxygen atom, The γ-butyrolactone ring in the formula has an α-substituted oxy-γ-butyrolactone derivative represented by (having at least one substituent other than the X—O— group described in the formula). 2. A non-aqueous electrochemical device comprising the electrolytic solution according to claim 1. 3. The non-aqueous electrochemical device according to claim 2, comprising at least two electrodes, a separator interposed between the two electrodes, and the electrolytic solution according to claim 1. 4. The following formula (1a): (In the formula, X ¹ is a hydrocarbon group which may have a substituent,
A heterocyclic group which may have a substituent or a nitrogen atom-containing group having a nitrogen atom at the binding site with Y is shown. Y is
Indicates an oxygen atom or a sulfur atom. R ¹ , R ² , R ³ , R ⁴ and R ⁵ are the same or different and represent a hydrogen atom, an optionally substituted hydrocarbon group or a substituted oxycarbonyl group. A plurality of R ¹ , R ² , R ³ , R ⁴ and R ⁵ may combine to form a ring together with 1 or 2 carbon atoms constituting a γ-butyrolactone ring. However, when Y is an oxygen atom and both R ² and R ³ are optionally substituted hydrocarbon groups, R ¹ is a hydrogen atom or an alkyl group, X ¹
Is an alkyl group) α-substituted oxy-γ-
Butyrolactone derivative. 5. X ¹ is (i) the following formula (1a-1): (In the formula, R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are the same or different and represent a hydrogen atom, an optionally substituted hydrocarbon group or a substituted oxycarbonyl group. ⁶ , R ⁷ , R
^A plurality of ⁸ , R ⁹ and R ¹⁰ may combine to form a ring together with 1 to 3 carbon atoms constituting the γ-butyrolactone ring. Provided that R ⁹ and R ¹⁰ are groups other than hydrogen atom), (ii) a saturated or unsaturated aliphatic hydrocarbon group, (iii) a hydrocarbon group containing an aryl group, or (iv ) The following formula (1a-2) [Chemical formula 4] (In the formula, R ¹¹ and R ¹² are the same or different and each represents a hydrogen atom, an optionally substituted hydrocarbon group, or a substituted oxycarbonyl group. R ¹¹ and R ¹² are bonded to each other. May form a double bond or a ring), the α-substituted oxy-γ-butyrolactone derivative according to claim 4. 6. The following formula (1b): (In the formula, X ² represents a hydrocarbon group which may have a substituent. X ³ and X ⁴ are the same or different and are a hydrogen atom or a hydrocarbon group which may have a substituent. R ¹ ,
R ² , R ³ , R ⁴ and R ⁵ are the same or different and each represent a hydrogen atom, a hydrocarbon group which may have a substituent, or a substituted oxycarbonyl group. R ¹ , R ² , R ³ , R ⁴ and R ⁵
May form a ring together with 1 to 3 carbon atoms forming a γ-butyrolactone ring by combining a plurality of them. However, alpha-substituted oxy -γ- butyrolactone derivative represented by R ⁴ and R ⁵ is a group other than a hydrogen atom). 7. The following formula (1c) [Chemical 6] (In the formula, X^FiveIs a hydrocarbon group which may have a substituent
Show. R¹, R², R³, R ^FourAnd R^FiveAre the same or different
A hydrogen atom, a hydrocarbon group which may have a substituent,
Alternatively, it represents a substituted oxycarbonyl group. R¹, R², R³,
R^FourAnd R^FiveIs a γ-butyrolactone ring formed by combining a plurality of
Forming a ring with 1 to 3 carbon atoms constituting
Good. However, R¹, R², R³, R^FourAnd R^FiveLess of
At least one has a fluorinated hydrocarbon group or substituent
Is an optionally substituted aryl group) α-substituted oxy
-Γ-butyrolactone derivative. 8. The following formula (1d) [Chemical 7] (In the formula, X⁶Is a hydrocarbon group which may have a substituent
Show. R¹, R², R³, R ^FourAnd R^FiveAre the same or different
A hydrogen atom, a hydrocarbon group which may have a substituent,
Alternatively, it represents a substituted oxycarbonyl group. R¹, R², R³,
R^FourAnd R^FiveIs a γ-butyrolactone ring formed by combining a plurality of
Forming a ring with 1 to 3 carbon atoms constituting
Good. However, R^FourAnd R^FiveIs a non-
Α-substituted oxy represented by (forming an aromatic ring)
-Γ-butyrolactone derivative. 9. The following formula (1e): (In the formula, X ⁷ represents a saturated hydrocarbon group which may have a substituent. R ² , R ³ , R ⁴ and R ⁵ are the same or different and each have a hydrogen atom or a substituent. A hydrocarbon group, which may be
Alternatively, it represents a substituted oxycarbonyl group. R ^2, R ^3, R ⁴ and R ^5, together with 1 to 3 carbon atoms a plurality constitutes a binding to γ- butyrolactone ring may form a ring. However, alpha-substituted oxy -γ- butyrolactone derivative represented by R ⁴ and R ⁵ is a group other than a hydrogen atom). 10. The following formula (1f) [Chemical 9] (In the formula, X⁸Is a hydrocarbon group which may have a substituent
Show. R¹, R², R³, R ^FourAnd R^FiveAre the same or different
A hydrogen atom, a hydrocarbon group which may have a substituent,
Alternatively, it represents a substituted oxycarbonyl group. R¹, R², R³,
R^FourAnd R^FiveIs a γ-butyrolactone ring formed by combining a plurality of
Forming a ring with 1 to 3 carbon atoms constituting
Good. However, R²Is a substituted oxycarbonyl group,
R^FourAnd R^FiveIs a group other than a hydrogen atom) α-
Substituted oxy-γ-butyrolactone derivative. 11. The following formula (1g) [Chemical 10] (In the formula, X⁹Is a hydrocarbon group which may have a substituent
Show. R¹, R², R³, R ^FourAnd R^FiveAre the same or different
A hydrogen atom, a hydrocarbon group which may have a substituent,
Alternatively, it represents a substituted oxycarbonyl group. R¹, R², R³,
R^FourAnd R^FiveIs a γ-butyrolactone ring formed by combining a plurality of
Forming a ring with 1 to 3 carbon atoms constituting
Good. However, R¹, R^FourAnd R^FiveIs a group other than hydrogen atom
Α-substituted oxy-γ-butyrolactone represented by
Derivative.