WO2018181907A1 - スルホン酸、カルボン酸又はそれらの塩 - Google Patents
スルホン酸、カルボン酸又はそれらの塩 Download PDFInfo
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- WO2018181907A1 WO2018181907A1 PCT/JP2018/013635 JP2018013635W WO2018181907A1 WO 2018181907 A1 WO2018181907 A1 WO 2018181907A1 JP 2018013635 W JP2018013635 W JP 2018013635W WO 2018181907 A1 WO2018181907 A1 WO 2018181907A1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/185—Saturated compounds having only one carboxyl group and containing keto groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
- C07C309/09—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton
- C07C309/10—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton containing etherified hydroxy groups bound to the carbon skeleton with the oxygen atom of at least one of the etherified hydroxy groups further bound to an acyclic carbon atom
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/70—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/72—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms
- C07C235/74—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atoms of the carboxamide groups bound to acyclic carbon atoms of a saturated carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/02—Sulfonic acids having sulfo groups bound to acyclic carbon atoms
- C07C309/03—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
- C07C309/07—Sulfonic acids having sulfo groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton containing oxygen atoms bound to the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C53/00—Saturated compounds having only one carboxyl group bound to an acyclic carbon atom or hydrogen
- C07C53/126—Acids containing more than four carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/235—Saturated compounds containing more than one carboxyl group
- C07C59/347—Saturated compounds containing more than one carboxyl group containing keto groups
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
Definitions
- the present invention relates to a sulfonic acid, a carboxylic acid or a salt thereof.
- Patent Document 1 describes a compound represented by the following formula.
- An object of the present invention is to provide a novel sulfonic acid, carboxylic acid or salt thereof having a carbonyl group.
- R 1 is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent.
- R 2 and R 4 be the case of 3 or more carbon atoms to form a ring include a monovalent or divalent heterocyclic ring, independently, .R 3 is H or a substituent group , An optionally substituted alkylene group having 1 to 10 carbon atoms, n is an integer of 1 or more, p and q are each independently an integer of 0 or more, and A is —SO 3 X or —COOX (X is H, a metal atom, NR 5 4 , an imidazolium which may have a substituent, a pyridinium which may have a substituent, or a substituent.
- R 5 is H or an organic group, which may be the same or different .
- L is a single bond, -CO 2 B - *, - OCO-B - *, - CONR 6 -B - *, - NR 6 CO-B- *, or, -CO- (where, -CO 2 -B -, - OCO -B -, - CONR 6 -B- and a carbonyl group contained in -NR 6 CO-B-), and B is a C 1-10 alkylene group which may have a single bond or a substituent, and R 6 is H or an optionally substituted alkyl group having 1 to 4 carbon atoms, * indicates the side bonded to A in the formula. It is a compound characterized by these.
- the compound preferably has a total number of carbon atoms of 3 to 30.
- L is preferably a single bond.
- R 2 and R 4 are preferably either H or a linear or branched alkyl group having 1 to 4 carbon atoms.
- R 3 is preferably an alkylene group having 1 to 4 carbon atoms having no substituent.
- R 1 is preferably a linear or branched alkyl group having 1 to 4 carbon atoms.
- the total of n, p and q is preferably an integer of 6 or more.
- R 1 is preferably a methyl group.
- X is preferably a metal atom or NR 5 4 (R 5 is as described above).
- the compound is preferably an aqueous dispersant.
- the compound of the present invention is a compound exhibiting a surface active action, and can be suitably used as an aqueous dispersant.
- the “organic group” means a group containing one or more carbon atoms or a group formed by removing one hydrogen atom from an organic compound.
- Examples of such “organic groups” An alkyl group optionally having one or more substituents, An alkenyl group optionally having one or more substituents, An alkynyl group optionally having one or more substituents, A cycloalkyl group optionally having one or more substituents, A cycloalkenyl group optionally having one or more substituents, A cycloalkadienyl group optionally having one or more substituents, An aryl group optionally having one or more substituents, An aralkyl group optionally having one or more substituents, A non-aromatic heterocyclic group optionally having one or more substituents, A heteroaryl group optionally having one or more substituents, A cyano group, Formyl group, RaO-, RaCO-, RaSO 2- , RaCOO-
- the “substituent” means a substitutable group.
- substitutable group examples include an aliphatic group, an aromatic group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aromatic oxy group, a heterocyclic oxy group, and an aliphatic oxycarbonyl group.
- the present invention provides the following formula: It is a compound characterized by these.
- R 1 is a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic alkyl group having 3 or more carbon atoms which may have a substituent. .
- R 1 is preferably a linear or molecular alkyl group having 1 to 4 carbon atoms.
- the alkyl group can include a monovalent or divalent heterocyclic ring, or can form a ring.
- the heterocyclic ring is preferably an unsaturated heterocyclic ring, more preferably an oxygen-containing unsaturated heterocyclic ring, and examples thereof include a furan ring.
- a divalent heterocycle may be inserted between two carbon atoms, or the divalent heterocycle may be bonded to —C ( ⁇ O) — located at the terminal, A monovalent heterocyclic ring may be located at the terminal of the alkyl group.
- the “carbon number” of the alkyl group includes the number of carbon atoms constituting the heterocyclic ring.
- the above compound preferably has a total number of carbon atoms of 3 to 30. Further, it is more preferably 5 to 25, and further preferably 7 to 20.
- alkyl group as R 1 may have include a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms, A hydroxy group is preferred, and a methyl group and an ethyl group are particularly preferred.
- the alkyl group as R 1 preferably does not contain a carbonyl group.
- 75% or less of hydrogen atoms bonded to carbon atoms may be substituted with halogen atoms, 50% or less may be substituted with halogen atoms, and 25% or less are substituted with halogen atoms.
- it is preferably a non-halogenated alkyl group that does not contain a halogen atom such as a fluorine atom or a chlorine atom.
- the alkyl group preferably does not have any substituents.
- R 1 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms which may have a substituent, or a cyclic alkyl group having 3 to 10 carbon atoms which may have a substituent. More preferably a linear or branched alkyl group having 1 to 10 carbon atoms not containing a carbonyl group or a cyclic alkyl group having 3 to 10 carbon atoms not containing a carbonyl group, and having no substituent.
- a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable, a linear or branched alkyl group having 1 to 3 carbon atoms having no substituent is still more preferable, and a methyl group (—CH 3 ) or an ethyl group (—C 2 H 5 ) is particularly preferred, and a methyl group (—CH 3 ) is most preferred.
- R 2 and R 4 are independently H or a substituent.
- a plurality of R 2 and R 4 may be the same or different.
- the substituent as R 2 and R 4 is preferably a halogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, or a hydroxy group.
- a group and an ethyl group are particularly preferred.
- the alkyl group as R 2 and R 4 preferably does not contain a carbonyl group.
- 75% or less of hydrogen atoms bonded to carbon atoms may be substituted with halogen atoms, 50% or less may be substituted with halogen atoms, and 25% or less are substituted with halogen atoms.
- it is preferably a non-halogenated alkyl group that does not contain a halogen atom such as a fluorine atom or a chlorine atom.
- the alkyl group preferably does not have any substituents.
- Examples of the alkyl group as R 2 and R 4 include a linear or branched alkyl group having 1 to 10 carbon atoms not containing a carbonyl group, or a cyclic alkyl group having 3 to 10 carbon atoms not containing a carbonyl group. More preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms which does not contain a carbonyl group, and a straight-chain or branched alkyl group having 1 to 3 carbon atoms which does not have a substituent. Is more preferable, and a methyl group (—CH 3 ) or an ethyl group (—C 2 H 5 ) is particularly preferable.
- R 2 and R 4 are independently preferably H or a linear or branched alkyl group having 1 to 10 carbon atoms which does not contain a carbonyl group, and H or a linear or molecular group having 1 to 4 carbon atoms
- a chain alkyl group is more preferable, and H or a linear or branched alkyl group having 1 to 3 carbon atoms having no substituent is more preferable, and H, a methyl group (—CH 3 ), or an ethyl group ( -C 2 H 5 ) is particularly preferred and H is most preferred.
- R 3 is preferably an alkylene group having 1 to 4 carbon atoms which has no substituent.
- R 3 is an alkylene group having 1 to 10 carbon atoms which may have a substituent. When a plurality of R 3 are present, they may be the same or different.
- the alkylene group preferably does not contain a carbonyl group.
- 75% or less of hydrogen atoms bonded to carbon atoms may be substituted with halogen atoms, 50% or less may be substituted with halogen atoms, and 25% or less are substituted with halogen atoms.
- it is preferably a non-halogenated alkyl group that does not contain a halogen atom such as a fluorine atom or a chlorine atom.
- the alkylene group preferably does not have any substituents.
- alkylene group examples include a linear or branched alkylene group having 1 to 10 carbon atoms which may have a substituent, or a cyclic alkylene group having 3 to 10 carbon atoms which may have a substituent.
- a linear or branched alkylene group having 1 to 10 carbon atoms not containing a carbonyl group or a cyclic alkylene group having 3 to 10 carbon atoms not containing a carbonyl group is preferable, and the number of carbons having no substituent.
- a linear or branched alkylene group of 1 to 10 is more preferable, and a methylene group (—CH 2 —), an ethylene group (—C 2 H 4 —), an isopropylene group (—CH (CH 3 ) CH 2 -) Or a propylene group (-C 3 H 6- ) is more preferable.
- R 1 , R 2 , R 3 and R 4 may be bonded to each other to form a ring.
- n is an integer of 1 or more. n is preferably an integer of 1 to 40, more preferably an integer of 1 to 30, and still more preferably an integer of 5 to 25.
- p and q are each independently an integer of 0 or more.
- p is preferably an integer of 0 to 10, more preferably 0 or 1.
- q is preferably an integer of 0 to 10, more preferably an integer of 0 to 5.
- n, p and q are preferably an integer of 6 or more in total.
- the total of n, p and q is more preferably an integer of 8 or more.
- the total of n, p and q is also preferably an integer of 60 or less, more preferably an integer of 50 or less, and still more preferably an integer of 40 or less.
- A represents —SO 3 X or —COOX
- X represents H, a metal atom, NR 5 4 , an imidazolium which may have a substituent, pyridinium which may have a substituent, or a substituted group.
- Phosphonium which may have a group R 5 is H or an organic group, which may be the same or different.
- R 5 is preferably H or an organic group having 1 to 10 carbon atoms, more preferably H or an organic group having 1 to 4 carbon atoms.
- the metal atom include alkali metals (Group 1), alkaline earth metals (Group 2), and Na, K, or Li is preferable.
- X is preferably H, a metal atom or NR 5 4, more preferably H, an alkali metal (Group 1), an alkaline earth metal (Group 2) or NR 5 4 , H, Na, K, Li or NH 4.
- an alkali metal Group 1
- an alkaline earth metal Group 2
- NR 5 4 NR 5 4
- H Na, K
- Li Li or NH 4.
- Na, K or NH 4 is even more preferred, Na or NH 4 is particularly preferred and NH 4 is most preferred.
- L represents a single bond, —CO 2 —B— *, —OCO—B— *, —CONR 6 —B— *, —NR 6 CO—B— *, or —CO— (where — CO 2 —B—, —OCO—B—, —CONR 6 —B— and —NR 6 CO—B— are excluded.),
- B may have a single bond or a substituent.
- Preferred is an alkylene group having 1 to 10 carbon atoms, and R 6 is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent.
- the alkylene group preferably has 1 to 5 carbon atoms.
- R 6 is more preferably H or a methyl group. * Indicates the side bonded to A in the formula.
- L is preferably a single bond.
- Examples of the compound include: CH 3 C (O) CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 COOK, CH 3 C (O) CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 COONa, CH 3 C (O) CH 2 CH 2 CH 2 CH 2 CH 2 COONa, CH 3 C (O) CH 2 CH 2 CH 2 CH 2 COONa, CH 3 C (O) CH 2 CH 2 CH 2 CH 2 COONa, CH 3 C (O) CH 2 CH 2 CH 2 COONa, CH 3 C (O) CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 COONa, CH 3 C (O) CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 COONa, CH 3 C (O) CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 COONa, CH 3 C (O) CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 CH 2 COONa, (CH 3 ) 3 CC (O) CH 2 CH 2
- the compound of the present invention has the following formula: (In the formula, R 1 , R 2 and n are as described above.) And a compound represented by the following formula: (Wherein R 3 is as described above. L is a single bond, —CO 2 —B— *, —OCO—B— *, —CONR 6 —B— *, —NR 6 CO—B—) *, Or —CO— (except for a carbonyl group contained in —CO 2 —B—, —OCO—B—, —CONR 6 —B—, —NR 6 CO—B—), and B Is an alkylene group having 1 to 10 carbon atoms which may have a single bond or a substituent, and R 6 is H or an alkyl group having 1 to 4 carbon atoms which may have a substituent.
- the reaction in step (11) can be carried out in the presence of a base.
- a base examples include sodium hydride, sodium hydroxide, potassium hydroxide, triethylamine and the like.
- the above base can be used in an amount of 0.5 to 20 mol relative to 1 mol of compound (10).
- the reaction in step (11) can be carried out in a solvent.
- a solvent an organic solvent is preferable and an aprotic polar solvent is more preferable.
- the organic solvent include ethers, aromatic compounds, nitriles, halogenated hydrocarbons, and the like.
- the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like. Among them, diethyl ether and tetrahydrofuran are preferable.
- the aromatic compound include benzene, toluene, xylene and the like, and among them, benzene is preferable.
- nitrile examples include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like, and among them, acetonitrile is preferable.
- halogenated hydrocarbon examples include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, and among them, dichloromethane and chloroform are preferable.
- the reaction temperature in the step (11) is preferably ⁇ 78 to 150 ° C., more preferably ⁇ 20 to 100 ° C.
- the reaction pressure in the step (11) is preferably 0 to 10 MPa, more preferably 0 to 1.0 MPa.
- the reaction time in the step (11) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.
- the compounds of the present invention may also have the following formula: (Wherein R 1 to R 4 , n, p and q are as defined above.
- L represents a single bond, —CO 2 —B— *, —OCO—B— *, —CONR 6 —B— *) , —NR 6 CO—B— * or —CO— (wherein —CO 2 —B—, —OCO—B—, —CONR 6 —B—, carbonyl group contained in —NR 6 CO—B—)
- B is a single bond or an alkylene group having 1 to 10 carbon atoms which may have a substituent, and R 6 has 1 carbon atom which may have H or a substituent.
- 4 is an alkyl group of ⁇ 4.
- the oxidation in the step (21) can be carried out by allowing a nitrosating agent to act on the compound (20).
- nitrosating agent sodium nitrite, nitrosylsulfuric acid, isoamyl nitrite and the like can be used.
- the nitrosating agent can be used in an amount of 0.5 to 10 mol per 1 mol of compound (20).
- the oxidation in step (21) can be carried out in a solvent.
- a solvent trifluoroacetic acid, acetonitrile and the like can be used.
- the oxidation temperature in the step (21) is preferably ⁇ 78 to 200 ° C., more preferably ⁇ 20 to 100 ° C.
- the pressure for oxidation in the step (21) is preferably 0 to 10 MPa, more preferably 0 to 1.0 MPa.
- the oxidation time in step (21) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 24 hours.
- R 11 represents H, a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a cyclic group having 3 or more carbon atoms which may have a substituent.
- the alkyl group may include a monovalent or divalent heterocyclic ring or may form a ring Y 1 is — (CR 2 2 ) n — or — (CR 2 2 ) n- (OR 3 ) p- (CR 4 2 ) q -L-CH 2- (R 2 to R 4 , n, L, p and q are as described above)).
- the compound (100) is hydroxylated to give the following formula: (Wherein R 11 and Y 1 are as described above), the step (101) for obtaining the compound (101) and the compound (101) are oxidized, and the following formula: (Wherein R 11 and Y 1 are as described above), and can be produced by a production method including the step (102) of obtaining the compound (102).
- the alkyl group as R 11 preferably does not contain a carbonyl group.
- 75% or less of the hydrogen atoms bonded to the carbon atom may be substituted with halogen atoms, 50% or less may be substituted with halogen atoms, and 25% or less are halogen atoms.
- it may be substituted by an atom, it is preferably a non-halogenated alkyl group that does not contain a halogen atom such as a fluorine atom or a chlorine atom.
- the alkyl group preferably does not have any substituents.
- R 11 is H, a linear or branched alkyl group having 1 to 9 carbon atoms which may have a substituent, or a cyclic group having 3 to 9 carbon atoms which may have a substituent.
- An alkyl group is preferable, and H, a linear or branched alkyl group having 1 to 9 carbon atoms that does not include a carbonyl group, or a cyclic alkyl group having 3 to 9 carbon atoms that does not include a carbonyl group is more preferable.
- a linear or branched alkyl group having 1 to 9 carbon atoms that does not have a substituent is more preferable, and H, a methyl group (—CH 3 ), or an ethyl group (—C 2 H 5 ) is even more preferable.
- H or a methyl group (—CH 3 ) is particularly preferable, and H is most preferable.
- Hydroxylation in the step (101) can be carried out by, for example, (1) a method in which phthalocyanine iron (II) (Fe (Pc)) and sodium borohydride are allowed to act on the compound (100) in an oxygen atmosphere, or (2) a compound ( 100) isopinocamphylborane (IpcBH 2 ) is allowed to act, and then the resulting intermediate (dialkylborane) is oxidized.
- II phthalocyanine iron
- Pc phthalocyanine iron
- sodium borohydride sodium borohydride
- IpcBH 2 isopinocamphylborane
- the amount of iron phthalocyanine (II) may be a catalytic amount, and can be used in an amount of 0.001 to 1.2 mol per 1 mol of the compound (100).
- sodium borohydride can be used in an amount of 0.5 to 20 mol relative to 1 mol of the compound (100).
- the reaction of method (1) can be carried out in a solvent.
- the solvent is preferably an organic solvent, and examples thereof include ethers, halogenated hydrocarbons, aromatic hydrocarbons, nitriles, and nitrogen-containing polar organic compounds.
- ether examples include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like. Among them, diethyl ether and tetrahydrofuran are preferable.
- halogenated hydrocarbon examples include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, and among them, dichloromethane and chloroform are preferable.
- aromatic hydrocarbon examples include benzene, toluene, xylene and the like, and among them, benzene and toluene are preferable.
- nitrile examples include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like, and among them, acetonitrile is preferable.
- nitrogen-containing polar organic compound examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like. Of these, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferable.
- the reaction temperature in method (1) is preferably ⁇ 78 to 200 ° C., more preferably 0 to 150 ° C.
- the reaction pressure in the method (1) is preferably from 0 to 5.0 MPa, more preferably from 0.1 to 1.0 MPa.
- the reaction time in method (1) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.
- isopinocampheylborane can be used in an amount of 1.0 to 10.0 mol with respect to 1 mol of the compound (100).
- the reaction of compound (100) with isopinocampheylborane can be carried out in a solvent.
- the solvent is preferably an organic solvent, and examples thereof include ethers, halogenated hydrocarbons, and aromatic hydrocarbons.
- ether examples include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like. Among them, diethyl ether and tetrahydrofuran are preferable.
- halogenated hydrocarbon examples include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, and among them, dichloromethane and chloroform are preferable.
- aromatic hydrocarbon examples include benzene, toluene, xylene and the like, and among them, benzene and toluene are preferable.
- reaction temperature between compound (100) and isopinocamphylborane is preferably ⁇ 78 to 200 ° C., more preferably 0 to 150 ° C.
- the pressure for the reaction between the compound (100) and isopinocampheylborane is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.
- the reaction time of the compound (100) and isopinocampheylborane is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.
- the oxidation in the method (2) can be carried out by allowing an oxidizing agent to act on the intermediate.
- the oxidizing agent include hydrogen peroxide.
- the oxidizing agent can be used in an amount of 0.7 to 10 mol relative to 1 mol of the intermediate.
- the oxidation in method (2) can be carried out in a solvent.
- the solvent include water, methanol, ethanol and the like, and water is particularly preferable.
- the oxidation temperature in the method (2) is preferably 0 to 100 ° C., more preferably 0 to 80 ° C.
- the pressure for oxidation in the method (2) is preferably from 0 to 5.0 MPa, more preferably from 0.1 to 1.0 MPa.
- the oxidation time in method (2) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.
- examples of the method for oxidizing compound (101) include (a) a method using Jones reagent (CrO 3 / H 2 SO 4 ) (Jones oxidation), (b) Dess-Martin periodinane ( DMP) (Dess-Martin oxidation), (c) Method using pyridinium chlorochromate (PCC), (d) A bleaching agent (NaOCl aqueous solution of about 5-6% in the presence of nickel compound such as NiCl 2 ) (E) a method in which a hydrogen acceptor such as an aldehyde or a ketone is allowed to act in the presence of an aluminum catalyst such as Al (CH 3 ) 3 or Al [OCH (CH 3 ) 2 ] 3 (Oppenauer oxidation) Is mentioned.
- a hydrogen acceptor such as an aldehyde or a ketone
- the oxidation in step (102) can be carried out in a solvent.
- a solvent water and an organic solvent are preferable, and water, a ketone, ether, a halogenated hydrocarbon, an aromatic hydrocarbon, a nitrile etc. are mentioned.
- ketone examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, and the like. Among these, acetone is preferable.
- ether examples include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like. Among them, diethyl ether and tetrahydrofuran are preferable.
- halogenated hydrocarbon examples include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, and among them, dichloromethane and chloroform are preferable.
- aromatic hydrocarbon examples include benzene, toluene, xylene and the like, and among them, benzene and toluene are preferable.
- nitrile examples include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like, and among them, acetonitrile is preferable.
- the oxidation temperature in step (102) is preferably ⁇ 78 to 200 ° C., and can be appropriately selected depending on the method employed.
- the oxidation pressure in the step (102) is preferably 0 to 5.0 MPa, and can be appropriately selected depending on the method employed.
- the oxidation time in the step (102) is preferably 0.1 to 72 hours, and can be appropriately selected depending on the method employed.
- Compound (10) and Compound (20) are also represented by the following formula: (In the formula, R 1 and Y 1 are as described above. R 101 is an organic group.)
- the compound (200) represented by ozonolysis is subjected to the following formula: (In formula, R ⁇ 1 > and Y ⁇ 1 > are as above.) It can manufacture by the manufacturing method including the process (201) which obtains the compound (201) shown.
- R 101 is preferably an alkyl group having 1 to 20 carbon atoms. Two R 101 may be the same or different.
- the ozonolysis in the step (201) can be carried out by applying ozone to the compound (200) and then post-treating with a reducing agent.
- Ozone can be generated by silent discharge in oxygen gas.
- Examples of the reducing agent used in the post-treatment include zinc, dimethyl sulfide, thiourea, and phosphines, and phosphines are preferable.
- the ozonolysis in the step (201) can be carried out in a solvent.
- a solvent water and an organic solvent are preferable, and water, alcohol, carboxylic acids, ether, a halogenated hydrocarbon, an aromatic hydrocarbon, etc. are mentioned.
- Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol and the like. Of these, methanol and ethanol are preferable.
- carboxylic acids examples include acetic acid and propionic acid. Of these, acetic acid is preferred.
- ether examples include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like. Among them, diethyl ether and tetrahydrofuran are preferable.
- halogenated hydrocarbon examples include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, and among them, dichloromethane and chloroform are preferable.
- aromatic hydrocarbon examples include benzene, toluene, xylene and the like, and among them, benzene and toluene are preferable.
- the temperature for ozonolysis in the step (201) is preferably ⁇ 78 to 200 ° C., more preferably 0 to 150 ° C.
- the pressure for ozonolysis in the step (201) is preferably 0 to 5.0 MPa, and more preferably 0.1 to 1.0 MPa.
- the time for ozonolysis in the step (201) is preferably 0.1 to 72 hours, and more preferably 0.1 to 48 hours.
- R 21 is also represented by the following formula: R 21 —CH ⁇ CH—Y 1 —OH (In the formula, Y 1 is as described above.
- R 21 has H, a linear or branched alkyl group having 1 or more carbon atoms which may have a substituent, or a substituent. Or a cyclic alkyl group having 3 or more carbon atoms, and when it has 3 or more carbon atoms, it may contain a monovalent or divalent heterocyclic ring or form a ring).
- the alkyl group as R 21 preferably does not contain a carbonyl group.
- 75% or less of the hydrogen atoms bonded to the carbon atom may be substituted with a halogen atom, 50% or less may be substituted with a halogen atom, and 25% or less is halogen.
- it may be substituted by an atom, it is preferably a non-halogenated alkyl group that does not contain a halogen atom such as a fluorine atom or a chlorine atom.
- the alkyl group preferably does not have any substituents.
- R 21 is H, a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, or a cyclic group having 3 to 8 carbon atoms which may have a substituent.
- An alkyl group is preferable, and H, a linear or branched alkyl group having 1 to 8 carbon atoms that does not include a carbonyl group, or a cyclic alkyl group having 3 to 8 carbon atoms that does not include a carbonyl group is more preferable.
- a linear or branched alkyl group having 1 to 8 carbon atoms having no substituent is more preferable, H or a methyl group (—CH 3 ) is particularly preferable, and H is most preferable.
- the alkyl group as R 22 preferably does not contain a carbonyl group.
- 75% or less of the hydrogen atoms bonded to the carbon atom may be substituted with halogen atoms, 50% or less may be substituted with halogen atoms, and 25% or less are halogen atoms.
- it may be substituted by an atom, it is preferably a non-halogenated alkyl group that does not contain a halogen atom such as a fluorine atom or a chlorine atom.
- the alkyl group preferably does not have any substituents.
- R 22 is a linear or branched alkyl group having 1 to 9 carbon atoms which may have a substituent, or a cyclic alkyl group having 3 to 9 carbon atoms which may have a substituent. More preferably a linear or branched alkyl group having 1 to 9 carbon atoms which does not contain a carbonyl group, or a cyclic alkyl group having 3 to 9 carbon atoms which does not contain a carbonyl group, and has no substituent.
- a linear or branched alkyl group having 1 to 9 carbon atoms is more preferred, a methyl group (—CH 3 ) or an ethyl group (—C 2 H 5 ) is particularly preferred, and a methyl group (—CH 3 ) is most preferred. preferable.
- Two R 22 may be the same or different.
- R 21 and R 22 preferably have a total carbon number of 1 to 7, more preferably 1 to 2, and most preferably 1.
- Epoxidation in the step (301) can be carried out by allowing an epoxidizing agent to act on the compound (300).
- the epoxidizing agent examples include perchloroacids such as metachloroperbenzoic acid (m-CPBA), perbenzoic acid, hydrogen peroxide, tert-butyl hydroperoxide, dimethyldioxirane, methyltrifluoromethyldioxirane, and the like. Of these, peracid is preferable, and metachloroperbenzoic acid is more preferable.
- the epoxidizing agent can be used in an amount of 0.5 to 10.0 mol per 1 mol of compound (300).
- the epoxidation in the step (301) can be carried out in a solvent.
- the solvent is preferably an organic solvent, and examples include ketones, ethers, halogenated hydrocarbons, aromatic hydrocarbons, nitriles, pyridines, nitrogen-containing polar organic compounds, dimethyl sulfoxide, and the like. Among these, dichloromethane is preferable.
- ketone examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, and the like. Among these, acetone is preferable.
- ether examples include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like. Among them, diethyl ether and tetrahydrofuran are preferable.
- halogenated hydrocarbon examples include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, and among them, dichloromethane and chloroform are preferable.
- aromatic hydrocarbon examples include benzene, toluene, xylene and the like, and among them, benzene and toluene are preferable.
- nitrile examples include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like, and among them, acetonitrile is preferable.
- nitrogen-containing polar organic compound examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like. Of these, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferable.
- the epoxidation temperature in the step (301) is preferably ⁇ 78 to 200 ° C., more preferably ⁇ 40 to 150 ° C.
- the epoxidation pressure in the step (301) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.
- the epoxidation time in step (301) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.
- the dialkyl copper lithium can be used in an amount of 0.5 to 10.0 moles relative to 1 mole of the compound (301).
- the reaction of step (302) can be carried out in a solvent.
- the solvent is preferably an organic solvent, and examples thereof include ethers, halogenated hydrocarbons, and aromatic hydrocarbons.
- ether examples include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like. Among them, diethyl ether and tetrahydrofuran are preferable.
- halogenated hydrocarbon examples include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, and among them, dichloromethane and chloroform are preferable.
- aromatic hydrocarbon examples include benzene, toluene, xylene and the like, and among them, benzene and toluene are preferable.
- the reaction temperature in the step (302) is preferably ⁇ 78 to 200 ° C., more preferably ⁇ 40 to 150 ° C.
- the reaction pressure in the step (302) is preferably 0 to 5.0 MPa, more preferably 0.1 to 1.0 MPa.
- the reaction time in the step (302) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.
- examples of the method for oxidizing compound (302) include (a) a method using Jones reagent (CrO 3 / H 2 SO 4 ) (Jones oxidation), (b) Dess-Martin periodinane ( DMP) (Dess-Martin oxidation), (c) Method using pyridinium chlorochromate (PCC), (d) A bleaching agent (NaOCl aqueous solution of about 5-6% in the presence of nickel compound such as NiCl 2 ) (E) a method in which a hydrogen acceptor such as an aldehyde or a ketone is allowed to act in the presence of an aluminum catalyst such as Al (CH 3 ) 3 or Al [OCH (CH 3 ) 2 ] 3 (Oppenauer oxidation) Is mentioned.
- a hydrogen acceptor such as an aldehyde or a ketone
- the oxidation in the step (303) can be carried out in a solvent.
- a solvent water and an organic solvent are preferable, and water, a ketone, alcohol, ether, a halogenated hydrocarbon, an aromatic hydrocarbon, a nitrile etc. are mentioned.
- ketone examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, diacetone alcohol, and the like. Among these, acetone is preferable.
- Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol and the like. Of these, methanol and ethanol are preferable.
- ether examples include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like. Among them, diethyl ether and tetrahydrofuran are preferable.
- halogenated hydrocarbon examples include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, and among them, dichloromethane and chloroform are preferable.
- aromatic hydrocarbon examples include benzene, toluene, xylene and the like, and among them, benzene and toluene are preferable.
- nitrile examples include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like, and among them, acetonitrile is preferable.
- the oxidation temperature in step (303) is preferably ⁇ 78 to 200 ° C., and can be appropriately selected depending on the method employed.
- the oxidation pressure in the step (303) is preferably 0 to 5.0 MPa, and can be appropriately selected depending on the method employed.
- the oxidation time in the step (303) is preferably 0.1 to 72 hours, and can be appropriately selected according to the method employed.
- Compound (10) and Compound (20) are also represented by the following formula: R 11 —CH ⁇ CH—Y 1 —OH (Wherein R 11 and Y 1 are as described above) and the compound (100) represented by the following formula: (Wherein R 11 and Y 1 are as described above), and can be produced by a production method including the step (401) of obtaining the compound (401).
- the oxidation in the step (401) can be carried out by allowing an oxidizing agent to act on the compound (100) in the presence of water and a palladium compound.
- the oxidizing agent examples include monovalent or divalent copper salts such as copper chloride, copper acetate, copper cyanide, trifluoromethanethiol copper, iron chloride, iron acetate, iron cyanide, trifluoromethanethiol iron, hexacyanoiron, sulfuric acid
- Iron salts such as iron, benzoquinones such as 1,4-benzoquinone, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, tetrachloro-1,2-benzoquinone, tetrachloro-1,4-benzoquinone , H 2 O 2 , MnO 2 , KMnO 4 , RuO 4 , m-chloroperbenzoic acid, peracetic acid, perbenzoic acid, tert-butyl hydroperoxide, cumene hydroperoxide, potassium persulfate, and potassium hydrogen persulfate -Potassium hydrogen sul
- copper salts, iron salts, benzoquinone, potassium hydrogen persulfate-potassium hydrogen sulfate-potassium sulfate mixtures, and oxygens are preferable, and copper chloride, iron chloride, 1,4-benzoquinone, and oxygen are more preferable.
- the oxidizing agent can be used in an amount of 0.001 to 10 mol with respect to 1 mol of the compound (100).
- the water can be used in an amount of 0.5 to 1000 mol with respect to 1 mol of the compound (100).
- the amount of the palladium compound is palladium dichloride.
- the amount of the palladium compound may be a catalytic amount, and can be used in an amount of 0.0001 to 1.0 mol with respect to 1 mol of the compound (100).
- the oxidation in the step (401) can be performed in a solvent.
- the solvent include water, esters, aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, carboxylic acids, ethers, halogenated hydrocarbons, nitrogen-containing polar organic compounds, nitriles, dimethyl sulfoxide, and sulfolane.
- ester examples include ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), and among them, ethyl acetate is preferable.
- PGMEA propylene glycol monomethyl ether acetate
- aliphatic hydrocarbon examples include hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, mineral spirit, etc. Among them, cyclohexane and heptane are preferable.
- aromatic hydrocarbon examples include benzene, toluene, xylene and the like, and among them, benzene and toluene are preferable.
- Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol and the like.
- carboxylic acids examples include acetic acid and propionic acid. Of these, acetic acid is preferred.
- ether examples include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like. Among them, diethyl ether and tetrahydrofuran are preferable.
- halogenated hydrocarbon examples include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, and among them, dichloromethane and chloroform are preferable.
- nitrogen-containing polar organic compound examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like. Of these, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone are preferable.
- nitrile examples include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like, and among them, acetonitrile is preferable.
- the oxidation temperature in the step (401) is preferably ⁇ 78 to 200 ° C., more preferably ⁇ 20 to 150 ° C.
- the oxidation pressure in the step (401) is preferably 0 to 10 MPa, more preferably 0.1 to 5.0 MPa.
- the oxidation time in the step (401) is preferably 0.1 to 72 hours, more preferably 0.1 to 48 hours.
- the compounds of the present invention may also have the following formula: R 11 —CH ⁇ CH— (CR 2 2 ) n — (OR 3 ) p — (CR 4 2 ) q —L—COOX Wherein R 2 to R 4 , R 11 , n, p, q and X are as described above.
- L is a single bond, —CO 2 —B— *, —OCO—B— *, —CONR 6 —B— *, —NR 6 CO—B— *, or —CO— (however, —CO 2 —B—, —OCO—B—, —CONR 6 —B—, —NR 6 CO—B—
- B is an alkylene group having 1 to 10 carbon atoms which may have a single bond or a substituent, and R 6 may have H or a substituent.
- the oxidation in the step (31) can be carried out by allowing an oxidizing agent to act on the compound (30) in the presence of water and a palladium compound, and the same conditions as the oxidation in the step (401) can be employed.
- the compounds of the present invention may also have the following formula: R 11 —CH ⁇ CH— (CR 2 2 ) n — (OR 3 ) p — (CR 4 2 ) q —CH ⁇ CH 2 (Wherein R 2 to R 4 , R 11 , n, p and q are as described above) are oxidized to give the following formula: (Wherein R 2 to R 4 , R 11 , n, p and q are as described above) (41) to obtain the compound (41), the compound (41) and sodium hydrogen sulfite React (R 2 to R 4 , R 11 , n, p, q, and X are as described above) can be produced by a production method including the step (42) of obtaining the compound (42).
- the oxidation in the step (41) can be carried out by allowing an oxidizing agent to act on the compound (40) in the presence of water and a palladium compound, and the same conditions as the oxidation in the step (401) can be employed.
- the sodium bisulfite in the reaction in the step (42), can be used in an amount of 0.001 to 20 mol relative to 1 mol of the compound (41).
- the reaction in step (42) can be carried out in the presence of azobisisobutyronitrile (AIBN).
- AIBN azobisisobutyronitrile
- Azobisisobutyronitrile can be used in an amount of 0.5 to 20 mol per 1 mol of compound (41).
- the reaction in step (42) can be carried out in a solvent.
- a solvent an organic solvent is preferable and an aprotic polar solvent is more preferable.
- the organic solvent include ethers, aromatic compounds, nitriles, halogenated hydrocarbons, and the like.
- the ether include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like. Among them, diethyl ether and tetrahydrofuran are preferable.
- the aromatic compound include benzene, toluene, xylene and the like, and among them, benzene is preferable.
- nitrile examples include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like, and among them, acetonitrile is preferable.
- halogenated hydrocarbon examples include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, and among them, dichloromethane and chloroform are preferable.
- the reaction temperature in the step (42) is preferably ⁇ 78 to 150 ° C., more preferably ⁇ 20 to 100 ° C.
- the reaction pressure in the step (42) is preferably 0 to 10 MPa, more preferably 0 to 1.0 MPa.
- the reaction time in the step (42) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.
- the compounds of the present invention may also have the following formula: R 11 —CH ⁇ CH— (CR 2 2 ) n — (OR 3 ) p — (CR 4 2 ) q —Z (Wherein R 2 to R 4 , R 11 , n, p, and q are as described above, Z is fluorine, chlorine, bromine, iodine) and compound (50) and compound (50-1) (Rx is a linear or branched alkyl group having 1 to 10 carbon atoms) And react with the following formula: (Wherein R 2 to R 4 , R 11 , Rx, n, p and q are as described above) (51) to obtain the compound (51) represented by the following formula (51) is obtained by oxidizing the compound (51): (Wherein R 2 to R 4 , R 11 , Rx, n, p and q are as described above) (52) to obtain the compound (52) represented by (Wherein R 2 to R 4 , R 11 , Rx, n,
- the reaction in step (51) can be carried out in the presence of a metal such as magnesium.
- the metal can be used in an amount of 0.5 to 20 mol relative to 1 mol of the compound (50).
- the reaction in step (52) can be carried out in a solvent.
- the solvent include water, esters, aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, carboxylic acids, ethers, halogenated hydrocarbons, nitrogen-containing polar organic compounds, nitriles, dimethyl sulfoxide, and sulfolane.
- ester examples include ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), and among them, ethyl acetate is preferable.
- PGMEA propylene glycol monomethyl ether acetate
- aliphatic hydrocarbon examples include hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, mineral spirit, etc. Among them, cyclohexane and heptane are preferable.
- aromatic hydrocarbon examples include benzene, toluene, xylene and the like, and among them, benzene and toluene are preferable.
- Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol and the like.
- carboxylic acids examples include acetic acid and propionic acid. Of these, acetic acid is preferred.
- ether examples include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like. Among them, diethyl ether and tetrahydrofuran are preferable.
- halogenated hydrocarbon examples include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, and among them, dichloromethane and chloroform are preferable.
- nitrogen-containing polar organic compound examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like. Among them, N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone are preferable.
- nitrile examples include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like, and among them, acetonitrile is preferable.
- the reaction temperature in the step (52) is preferably ⁇ 78 to 150 ° C., more preferably ⁇ 20 to 100 ° C.
- the reaction pressure in the step (52) is preferably 0 to 10 MPa, more preferably 0 to 1.0 MPa.
- the reaction time in the step (52) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.
- the oxidation in the step (52) can be carried out by allowing an oxidizing agent to act on the compound (51) in the presence of water and a palladium compound, and the same conditions as the oxidation in the step (401) can be employed.
- the hydrolysis in the step (53) can be performed by a known method.
- it can be performed by the action of an aqueous sodium hydroxide solution.
- the compounds of the present invention may also have the following formula: (Wherein R 2 to R 4 , R 11 , n, p and q are as described above) and glycine are reacted to give the following formula: (Wherein R 2 to R 4 , R 11 , n, p and q are as defined above) (61), wherein the compound (61) is obtained by oxidizing the compound (61) (Wherein R 2 to R 4 , R 11 , n, p and q are as described above) can be produced by a production method including a step (62) for obtaining a compound (62) represented by the following formula (62).
- the reaction in step (61) can be carried out in the presence of a base.
- a base examples include sodium hydride, sodium hydroxide, potassium hydroxide, triethylamine and the like.
- the above base can be used in an amount of 0.5 to 20 mol relative to 1 mol of compound (10).
- the reaction in step (61) can be carried out in a solvent.
- the solvent include water, esters, aliphatic hydrocarbons, aromatic hydrocarbons, alcohols, carboxylic acids, ethers, halogenated hydrocarbons, nitrogen-containing polar organic compounds, nitriles, dimethyl sulfoxide, and sulfolane.
- ester examples include ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), and among them, ethyl acetate is preferable.
- PGMEA propylene glycol monomethyl ether acetate
- aliphatic hydrocarbon examples include hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, mineral spirit, etc. Among them, cyclohexane and heptane are preferable.
- aromatic hydrocarbon examples include benzene, toluene, xylene and the like, and among them, benzene and toluene are preferable.
- Examples of the alcohol include methanol, ethanol, 1-propanol, isopropanol and the like.
- carboxylic acids examples include acetic acid and propionic acid. Of these, acetic acid is preferred.
- ether examples include diethyl ether, tetrahydrofuran, dioxane, diethylene glycol diethyl ether, and the like. Among them, diethyl ether and tetrahydrofuran are preferable.
- halogenated hydrocarbon examples include dichloromethane, dichloroethane, chloroform, chlorobenzene, o-dichlorobenzene, and among them, dichloromethane and chloroform are preferable.
- nitrogen-containing polar organic compound examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like. Among them, N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone are preferable.
- nitrile examples include acetonitrile, propionitrile, butyronitrile, isobutyronitrile, benzonitrile and the like, and among them, acetonitrile is preferable.
- the reaction temperature in the step (61) is preferably ⁇ 78 to 150 ° C., more preferably ⁇ 20 to 100 ° C.
- the reaction pressure in the step (61) is preferably 0 to 10 MPa, more preferably 0 to 1.0 MPa.
- the reaction time in the step (61) is preferably from 0.1 to 72 hours, more preferably from 0.1 to 48 hours.
- the oxidation in the step (62) can be carried out by allowing an oxidizing agent to act on the compound (61) in the presence of water and a palladium compound, and the same conditions as the oxidation in the step (401) can be employed.
- the purity of the resulting compound may be increased by distilling off the solvent, performing distillation, purification, or the like after completion of each step.
- the obtained compound is a compound in which X is H, such as —SO 3 H, —COOH, and the like, these groups can be converted into a salt form by contacting with an alkali such as sodium carbonate or ammonia.
- Example 1 11-Hydroxyundecan-2-one (1.86 g) and THF were added to the flask, and the mixture was stirred at 0 ° C. 60% NaH (0.4 g) was gradually added thereto, and then stirred for 30 minutes. Thereafter, a THF solution of propane sultone (1.22 g) was gradually added dropwise, and then the mixture was stirred at 40 ° C. for 10 hours. Then, diethyl ether was added and filtered to obtain 1.65 g (yield 50%) of the target sodium 3-((10-oxoundecyl) oxy) propane-1-sulfonate.
- Example 2 A mixture of 10-undecenoic acid (4.7 g), 1,4-benzoquinone (0.63 g), DMF (50 mL), water (5 mL) and PdCl 2 (0.09 g) was heated and stirred at 90 ° C. for 12 hours. Thereafter, the solvent was distilled off under reduced pressure. Sodium methoxide methanol solution was added to the resulting residue, hydrochloric acid was added to the filtered solid, extracted with ethyl acetate, dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 10-oxoundecanoic acid (3.2 g).
- Example 4 1,10-undecadiene (6.55 g), dimethylformamide (300 ml), water (43 ml), palladium chloride (0.38 g), iron (III) sulfate n hydrate (25.8 g) were added to the reactor. The mixture was heated and stirred at ° C. Thereafter, liquid separation, dehydration, concentration and purification by silica gel column chromatography were performed to obtain 10-undecen-2-one (3.17 g) in a yield of 44%.
- Example 5 Sodium 11-oxododecanesulfonate was synthesized in the same manner as in Example 1 except that the raw material was changed from 1,10-undecadiene to 1,11-dodecadiene.
- Example 6 Magnesium (shaved, 8.32 g, 342.1 mmol) and THF (20 mL) were added to the reactor, and 11-bromoundecene (11.95 g, 102.6 mmol) diluted with THF (100 mL) was slowly added dropwise. Then, it heated at 70 degreeC. Thereafter, the reaction solution was added dropwise to a mixed solution of diethyl oxalate (10.0 g, 68.4 mmol) and THF (70 mL) cooled at ⁇ 78 ° C. Then, it heated up to room temperature and added and saturated ammonium chloride aqueous solution (150 mL).
- Example 7 Glycine (3.2 g) and aqueous sodium hydroxide solution (85 mL) were added to the reactor, and a solution of 10-undecenoyl chloride (5.7 g) in THF was added dropwise with stirring at 0 ° C., and the mixture was further stirred at room temperature. After completion of the reaction, the reaction mixture was quenched with hydrochloric acid, and purified by liquid separation and recrystallization to obtain 2- (10-undecenamide) acetic acid (4.8 g) in a yield of 71%.
- the reactor was charged with a mixture of 2- (10-undecenamide) acetic acid (4.8 g), N, N-dimethylacetamide (80 mL), water (8.0 mL) and PdCl 2 (0.18 g).
- the mixture was heated and stirred at 80 ° C. for 24 hours in an oxygen atmosphere (0.1 MPa).
- the mixture was separated and purified by recrystallization to obtain 2- (10-oxoundecanamido) acetic acid (1.5 g) in a yield of 29%.
- Example 7 Sodium 3-((10-oxoundecyl) oxy) propane-1-sulfonate obtained in Example 1, ammonium 10-oxoundecanoate obtained in Example 2, and 10-oxoundecanoic acid obtained in Example 3 Potassium, sodium 10-oxoundecanesulfonate obtained in Example 4, sodium 11-oxododecanesulfonate obtained in Example 5, sodium 2,12-dioxotridecanoate obtained in Example 6, and The potassium 2- (10-oxoundecanamido) acetate obtained in Example 7 was dissolved in water to the concentration shown in Table 1, and the surface tension was measured. The surface tension was measured at 20 ° C. by the Wilhelmy method. The results are shown in Table 1.
- the compound of the present invention can suitably reduce the surface tension of water.
- the compound of the present invention can be suitably used as a surfactant.
- the compound of the present invention can be suitably used as an interfacial accelerator (particularly an interfacial accelerator in paints, lacquers, adhesives, etc.).
- the compound of the present invention can also be suitably used, for example, as a viscosity reducing agent.
- the compound of the present invention can also be suitably used, for example, as a dispersant, particularly an aqueous dispersant.
- the compound of the present invention can also be suitably used, for example, as an emulsifier.
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Abstract
Description
で示されることを特徴とする化合物である。
当該「有機基」の例は、
1個以上の置換基を有していてもよいアルキル基、
1個以上の置換基を有していてもよいアルケニル基、
1個以上の置換基を有していてもよいアルキニル基、
1個以上の置換基を有していてもよいシクロアルキル基、
1個以上の置換基を有していてもよいシクロアルケニル基、
1個以上の置換基を有していてもよいシクロアルカジエニル基、
1個以上の置換基を有していてもよいアリール基、
1個以上の置換基を有していてもよいアラルキル基、
1個以上の置換基を有していてもよい非芳香族複素環基、
1個以上の置換基を有していてもよいヘテロアリール基、
シアノ基、
ホルミル基、
RaO-、
RaCO-、
RaSO2-、
RaCOO-、
RaNRaCO-、
RaCONRa-、
RaOCO-、及び
RaOSO2-
(これらの式中、Raは、独立して、
1個以上の置換基を有していてもよいアルキル基、
1個以上の置換基を有していてもよいアルケニル基、
1個以上の置換基を有していてもよいアルキニル基、
1個以上の置換基を有していてもよいシクロアルキル基、
1個以上の置換基を有していてもよいシクロアルケニル基、
1個以上の置換基を有していてもよいシクロアルカジエニル基、
1個以上の置換基を有していてもよいアリール基、
1個以上の置換基を有していてもよいアラルキル基、
1個以上の置換基を有していてもよい非芳香族複素環基、又は
1個以上の置換基を有していてもよいヘテロアリール基である)
を包含する。
上記有機基としては、1個以上の置換基を有していてもよいアルキル基が好ましい。
上記アルキル基は、炭素数が3以上の場合は1価又は2価の複素環を含むこともできるし、環を形成することもできる。上記複素環としては、不飽和複素環が好ましく、含酸素不飽和複素環がより好ましく、例えば、フラン環等が挙げられる。R1において、2価の複素環が2つの炭素原子間に挿入されていてもよいし、2価の複素環が末端に位置して-C(=O)-と結合してもよいし、1価の複素環が上記アルキル基の末端に位置してもよい。
上記アルキル基は、炭素原子に結合した水素原子の75%以下がハロゲン原子により置換されていてもよく、50%以下がハロゲン原子により置換されていてもよく、25%以下がハロゲン原子により置換されていてもよいが、フッ素原子、塩素原子等のハロゲン原子を含まない非ハロゲン化アルキル基であることが好ましい。
上記アルキル基は、如何なる置換基も有していないことが好ましい。
上記アルキル基は、炭素原子に結合した水素原子の75%以下がハロゲン原子により置換されていてもよく、50%以下がハロゲン原子により置換されていてもよく、25%以下がハロゲン原子により置換されていてもよいが、フッ素原子、塩素原子等のハロゲン原子を含まない非ハロゲン化アルキル基であることが好ましい。
上記アルキル基は、如何なる置換基も有していないことが好ましい。
上記アルキレン基は、炭素原子に結合した水素原子の75%以下がハロゲン原子により置換されていてもよく、50%以下がハロゲン原子により置換されていてもよく、25%以下がハロゲン原子により置換されていてもよいが、フッ素原子、塩素原子等のハロゲン原子を含まない非ハロゲン化アルキル基であることが好ましい。
上記アルキレン基は、如何なる置換基も有していないことが好ましい。
Xとしては、H、金属原子又はNR5 4が好ましく、H、アルカリ金属(1族)、アルカリ土類金属(2族)又はNR5 4がより好ましく、H、Na、K、Li又はNH4が更に好ましく、Na、K又はNH4が更により好ましく、Na又はNH4が特に好ましく、NH4が最も好ましい。
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2COOK、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2COONa、
CH3C(O)CH2CH2CH2CH2CH2CH2COONa、
CH3C(O)CH2CH2CH2CH2CH2COONa、
CH3C(O)CH2CH2CH2CH2COONa、
CH3C(O)CH2CH2CH2COONa、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2COONa、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2COONa、
(CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa、
(CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa、
(CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa、
CH3CH2C(O)CH2CH2CH2CH2CH2CH2CH2COONa、
CH3CH2CH2C(O)CH2CH2CH2CH2CH2CH2COONa、
CH3CH2CH2CH2C(O)CH2CH2CH2CH2CH2COONa、
CH3CH2CH2CH2CH2C(O)CH2CH2CH2CH2COONa、
CH3CH2CH2CH2CH2CH2C(O)CH2CH2CH2COONa、
CH3CH2CH2CH2CH2CH2CH2C(O)CH2CH2COONa、
CH3CH2CH2CH2CH2CH2CH2CH2C(O)CH2COONa、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2COONa、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2COOK、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2COOK、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2COONa、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2COONa、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONa、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COOH、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COOLi、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(O)COONH4、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2COONa、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2C(CH3)2COOK、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2SO3Na、
CH3C(O)CH2CH2CH2CH2CH2CH2SO3Na、
CH3C(O)CH2CH2CH2CH2CH2SO3Na、
CH3C(O)CH2CH2CH2CH2SO3Na、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、
(CH3)3CC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、
(CH3)2CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、(CH2)5CHC(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2SO3Na、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2SO3Na、
CH3C(O)CH2CH2CH2CH2CH2CH2SO3Na、
CH3C(O)CH2CH2CH2CH2CH2SO3Na、
CH3C(O)CH2CH2CH2CH2SO3Na、
CH3C(O)CH2CH2CH2SO3Na、
CH3C(O)CH2CH2SO3Na、
CH3C(O)CH2SO3Na、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OCH2CH2CH2SO3Na、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)NHCH2SO3Na、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2NHC(O)CH2SO3Na、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)SO3Na、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2C(O)OCH2SO3Na、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2OC(O)CH2SO3Na、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3H、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3K、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3Li、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2CH2SO3NH4、
CH3C(O)CH2CH2CH2CH2CH2CH2CH2CH2C(CH3)2SO3Na
等が挙げられる。
で示される化合物(10)と、下記式:
で示される化合物(11)を得る工程(11)を含む製造方法により、好適に製造できる。
上記塩基としては、水素化ナトリウム、水酸化ナトリウム、水酸化カリウム、トリエチルアミン等が挙げられる。上記塩基は、化合物(10)1モルに対して、0.5~20モルの量で使用できる。
上記溶媒としては、有機溶媒が好ましく、非プロトン性極性溶媒がより好ましい。上記有機溶媒としては、エーテル、芳香族化合物、ニトリル、ハロゲン化炭化水素等が挙げられる。
上記エーテルとしては、ジエチルエーテル、テトラヒドロフラン、ジオキサン、ジエチレングリコールジエチルエーテル等が挙げられ、なかでも、ジエチルエーテル、テトラヒドロフランが好ましい。
上記芳香族化合物としては、ベンゼン、トルエン、キシレン等が挙げられ、なかでも、ベンゼンが好ましい。
上記ニトリルとしては、アセトニトリル、プロピオニトリル、ブチロニトリル、イソブチロニトリル、ベンゾニトリル等が挙げられ、なかでも、アセトニトリルが好ましい。
上記ハロゲン化炭化水素としては、ジクロロメタン、ジクロロエタン、クロロホルム、クロロベンゼン、o-ジクロロベンゼン等が挙げられ、なかでも、ジクロロメタン、クロロホルムが好ましい。
で示される化合物(20)を酸化させて、下記式:
で示される化合物(21)を得る工程(21)を含む製造方法により、好適に製造できる。
R11-CH=CH-Y1-OH
(式中、R11は、H、置換基を有してもよい炭素数1以上の直鎖状若しくは分岐鎖状のアルキル基、又は、置換基を有してもよい炭素数3以上の環状のアルキル基であり、炭素数が3以上の場合は1価又は2価の複素環を含んでも環を形成していてもよい。Y1は、-(CR2 2)n-又は-(CR2 2)n-(OR3)p-(CR4 2)q-L-CH2-(R2~R4、n、L、p及びqは、上記のとおり。)である。)で示される化合物(100)をヒドロキシ化して、下記式:
R11としての上記アルキル基は、炭素原子に結合した水素原子の75%以下がハロゲン原子により置換されていてもよく、50%以下がハロゲン原子により置換されていてもよく、25%以下がハロゲン原子により置換されていてもよいが、フッ素原子、塩素原子等のハロゲン原子を含まない非ハロゲン化アルキル基であることが好ましい。
上記アルキル基は、如何なる置換基も有していないことが好ましい。
R21-CH=CH-Y1-OH
(式中、Y1は、上記のとおり。R21は、H、置換基を有してもよい炭素数1以上の直鎖状若しくは分岐鎖状のアルキル基、又は、置換基を有してもよい炭素数3以上の環状のアルキル基であり、炭素数が3以上の場合は1価又は2価の複素環を含んでも環を形成していてもよい。)で示される化合物(300)をエポキシ化して、下記式:
R21としての上記アルキル基は、炭素原子に結合した水素原子の75%以下がハロゲン原子により置換されていてもよく、50%以下がハロゲン原子により置換されていてもよく、25%以下がハロゲン原子により置換されていてもよいが、フッ素原子、塩素原子等のハロゲン原子を含まない非ハロゲン化アルキル基であることが好ましい。
上記アルキル基は、如何なる置換基も有していないことが好ましい。
R22としての上記アルキル基は、炭素原子に結合した水素原子の75%以下がハロゲン原子により置換されていてもよく、50%以下がハロゲン原子により置換されていてもよく、25%以下がハロゲン原子により置換されていてもよいが、フッ素原子、塩素原子等のハロゲン原子を含まない非ハロゲン化アルキル基であることが好ましい。
上記アルキル基は、如何なる置換基も有していないことが好ましい。
上記エポキシ化剤は、化合物(300)1モルに対して、0.5~10.0モルの量で使用できる。
R11-CH=CH-Y1-OH
(式中、R11及びY1は、上記のとおり。)で示される化合物(100)を酸化して、下記式:
上記酸化剤は、化合物(100)1モルに対して、0.001~10モルの量で使用できる。
R11-CH=CH-(CR2 2)n-(OR3)p-(CR4 2)q-L-COOX
(式中、R2~R4、R11、n、p、q及びXは、上記のとおり。Lは、単結合、-CO2-B-*、-OCO-B-*、-CONR6-B-*、-NR6CO-B-*、又は、-CO-(但し、-CO2-B-、-OCO-B-、-CONR6-B-、-NR6CO-B-に含まれるカルボニル基を除く。)であり、Bは単結合もしくは置換基を有してもよい炭素数1から10のアルキレン基であり、R6は、H又は置換基を有していてもよい、炭素数1~4のアルキル基である。*は、式中の-COOXに結合する側を指す。)で示される化合物(30)を酸化して、下記式:
R11-CH=CH-(CR2 2)n-(OR3)p-(CR4 2)q-CH=CH2
(式中、R2~R4、R11、n、p及びqは、上記のとおり。)で示される化合物(40)を酸化して、下記式:
アゾビスイソブチロニトリルは、化合物(41)1モルに対して、0.5~20モルの量で使用できる。
上記溶媒としては、有機溶媒が好ましく、非プロトン性極性溶媒がより好ましい。上記有機溶媒としては、エーテル、芳香族化合物、ニトリル、ハロゲン化炭化水素等が挙げられる。
上記エーテルとしては、ジエチルエーテル、テトラヒドロフラン、ジオキサン、ジエチレングリコールジエチルエーテル等が挙げられ、なかでも、ジエチルエーテル、テトラヒドロフランが好ましい。
上記芳香族化合物としては、ベンゼン、トルエン、キシレン等が挙げられ、なかでも、ベンゼンが好ましい。
上記ニトリルとしては、アセトニトリル、プロピオニトリル、ブチロニトリル、イソブチロニトリル、ベンゾニトリル等が挙げられ、なかでも、アセトニトリルが好ましい。
上記ハロゲン化炭化水素としては、ジクロロメタン、ジクロロエタン、クロロホルム、クロロベンゼン、o-ジクロロベンゼン等が挙げられ、なかでも、ジクロロメタン、クロロホルムが好ましい。
R11-CH=CH-(CR2 2)n-(OR3)p-(CR4 2)q-Z
(式中、R2~R4、R11、n、p及びqは、上記のとおり。Zはフッ素、塩素、臭素、ヨウ素)で示される化合物(50)と化合物(50-1)
を反応させて、下記式:
上記金属は、化合物(50)1モルに対して、0.5~20モルの量で使用できる。
上記溶媒としては、水、エステル、脂肪族炭化水素、芳香族炭化水素、アルコール、カルボン酸類、エーテル、ハロゲン化炭化水素、含窒素極性有機化合物、ニトリル、ジメチルスルホキシド、スルホランが挙げられる。
上記塩基としては、水素化ナトリウム、水酸化ナトリウム、水酸化カリウム、トリエチルアミン等が挙げられる。上記塩基は、化合物(10)1モルに対して、0.5~20モルの量で使用できる。
上記溶媒としては、水、エステル、脂肪族炭化水素、芳香族炭化水素、アルコール、カルボン酸類、エーテル、ハロゲン化炭化水素、含窒素極性有機化合物、ニトリル、ジメチルスルホキシド、スルホランが挙げられる。
フラスコに11-ヒドロキシウンデカン-2-オン(1.86g)とTHFを加え0℃にて撹拌した。そこに60%NaH(0.4g)を徐々に加え、その後30分撹拌した。その後、プロパンサルトン(1.22g)のTHF溶液を徐々に滴下し、その後、40℃にて10時間撹拌した。その後、ジエチルエーテルを加え、濾過することで目的の3-((10-オキソウンデシル)オキシ)プロパン-1-スルホン酸ナトリウムを1.65g(収率50%)得た。
10-ウンデセン酸(4.7g)、1,4-ベンゾキノン(0.63g)、DMF(50mL)、水(5mL)及びPdCl2(0.09g)の混合物を90℃で12時間加熱撹拌した。
その後減圧下に溶媒を留去した。得られた残渣にナトリウムメトキシドメタノール溶液を加え、濾取した固体に塩酸を加え、酢酸エチルで抽出し、硫酸ナトリウムで乾燥し、減圧下に溶媒を留去した。残渣をカラムクロマトグラフィーで精製し、10-オキソウンデカン酸(3.2g)を得た。
得られた10-オキソウンデカン酸のスペクトルデータを以下に示す。
1H-NMR(CDCl3) δppm:1.27-1.37(m,8H)、1.51-1.60(m,4H)、2.11(s,3H)、2.29-2.42(m,4H)
得られた10-オキソウンデカン酸アンモニウムのスペクトルデータを以下に示す。
1H-NMR(CDCl3) δppm:1.05(m,8H)、1.31(m,4H)、1.96-2.02(m,5H)、2.28-2.34(t,J=7.3,4H)
10-オキソウンデカン酸(1.8g)を1.0MKOH水に加えて、水を留去して、10-オキソウンデカン酸カリウム(2.2g)を得た。
得られた10-オキソウンデカン酸カリウムのスペクトルデータを以下に示す。
1H-NMR(CDCl3) δppm:1.04(m,8H)、1.30-1.32(m,4H)、1.89-2.01(m,5H)、2.27-2.33(t,J=7.6,4H)
反応器に1,10-ウンデカジエン(6.55g)、ジメチルホルムアミド(300ml)、水(43ml)、塩化パラジウム(0.38g)、硫酸鉄(III)n水和物(25.8g)を加え45℃で加熱撹拌した。その後、分液、脱水、濃縮およびシリカゲルカラムクロマトグラフィー精製を行い10-ウンデセン-2-オン(3.17g)を収率44%で得た。
次に、反応器に10-ウンデセン-2-オン(1.29g)、メタノール(54ml)、水(27ml)、亜硫酸水素ナトリウム(1.07g)、アゾビスイソブチロニトリル(0.13g)を加え80℃で加熱撹拌した。生成した反応混合物を再結晶することで10-オキソウンデカンスルホン酸ナトリウム(0.41g)を収率19%で得た。
原料を1,10-ウンデカジエンから1,11-ドデカジエンに変更した点を除いて、実施例1と同様の方法で、11-オキソドデカンスルホン酸ナトリウムを合成した。
反応器にマグネシウム(削り状、8.32g、342.1mmol)、THF(20mL)を加え、THF(100mL)で希釈した11-ブロモウンデセン(11.95g、102.6mmol)をゆっくりと滴下した。その後、70°Cに加熱した。その後、-78℃で冷却したシュウ酸ジエチル(10.0g、68.4mmol)、THF(70mL)の混合液に当該反応液を滴下した。その後、室温まで昇温させ、飽和塩化アンモニウム水溶液(150mL)を加えクエンチした。その後、分液、脱水、濃縮およびシリカゲルカラムクロマトグラフィー精製を行い、8.07g(収率46.3%)の2-オキソトリデ-12-セン酸エチル(無色透明液体)を得た。
反応器に2-オキソトリデ-12-セン酸エチル(8.62g、33.9mmol)、DMAc(20mL)、イオン交換水(2.0mL)、ベンゾキノン(3.66g、33.9mmol)、PdCl2(30.0mg、0.169mmol)を加え、40度℃で加熱撹拌した。その後、分液、脱水、濃縮およびシリカゲルカラムクロマトグラフィー精製を行い、2,12-ジオキソトリデカン酸エチル(4.54g)4.54gを収率50%で得た。
続いて、反応器に2,12-ジオキソトリデカン酸エチル(3.63g、13.4mmol)、1.0M HCl水溶液(50mL)を加え、110°Cで加熱撹拌した。その後、分液、乾燥および濃縮を行い、2,12-ジオキソトリデカン酸(3.17g)を得た。その後、1.0M NaOH水溶液を作用させ2,12-ジオキソトリデカン酸ナトリウムをquantで得た。
反応器にグリシン(3.2g)、水酸化ナトリウム水溶液(85mL)を加え、0℃攪拌下、10-ウンデセノイルクロリド(5.7g)のTHF溶液を滴下、さらに室温で攪拌した。反応終了後、塩酸でクエンチし、分液、再結晶で精製し、2-(10-ウンデセンアミド)酢酸(4.8g)を収率71%で得た。
次に、反応器に2-(10-ウンデセンアミド)酢酸(4.8g)、N,N-ジメチルアセトアミド(80mL)、水(8.0mL)及びPdCl2(0.18g)の混合物を、酸素雰囲気下(0.1MPa)、80℃で24時間加熱攪拌した。反応終了後、分液、再結晶で精製し、2-(10-オキソウンデカンアミド)酢酸(1.5g)を収率29%で得た。
この2-(10-オキソウンデカンアミド)酢酸(1.5g)のエタノール/水混合溶液に、0.5M KOHエタノール溶液(11mL)を滴下、攪拌後、室温で減圧下溶媒留去し、2-(10-オキソウンデカンアミド)酢酸カリウム(1.8g)を白色固体として得た。
本発明の化合物は、界面活性剤として好適に使用できる。
本発明の化合物は、界面促進剤(特に、塗料、ラッカー、又は接着剤等における界面促進剤)として好適に使用できる。
本発明の化合物は、また例えば、粘性低下剤として好適に使用できる。
本発明の化合物は、また例えば、分散剤、特に水系分散剤として好適に使用できる。
本発明の化合物は、また例えば、乳化剤として好適に使用できる。
Claims (10)
- 下記式:
で示されることを特徴とする化合物。 - 炭素数の総数が3~30である請求項1記載の化合物。
- 前記Lは単結合である請求項1又は2記載の化合物。
- 前記R2及びR4がH、炭素数1~4の直鎖状若しくは分岐鎖状のアルキル基のいずれかである請求項1、2又は3記載の化合物。
- 前記R3が置換基を有さない炭素数1~4のアルキレン基である請求項1、2、3又は4記載の化合物。
- 前記R1が炭素数1~4の直鎖状又は分岐鎖状のアルキル基である請求項1、2、3、4又は5記載の化合物。
- 前記式中、n、p及びqの合計が6以上の整数である請求項1、2、3、4、5又は6記載の化合物。
- 前記式中、R1はメチル基である請求項1、2、3、4、5、6又は7記載の化合物。
- 前記式中、Xは金属原子又はNR5 4(R5は前記のとおり)である請求項1、2、3、4、5、6、7又は8記載の化合物。
- 水系分散剤である請求項1、2、3、4、5、6、7、8又は9記載の化合物。
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US16/495,641 US11440875B2 (en) | 2017-03-31 | 2018-03-30 | Sulfonic acid, carboxylic acid, and salts thereof |
CN201880020221.1A CN110461815A (zh) | 2017-03-31 | 2018-03-30 | 磺酸、羧酸或它们的盐 |
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