Classifications

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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
  • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
  • C07C211/52—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring the carbon skeleton being further substituted by halogen atoms or by nitro or nitroso groups
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
  • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
  • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
  • C07C211/53—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having the nitrogen atom of at least one of the amino groups further bound to a hydrocarbon radical substituted by amino groups
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  • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
  • C07C33/40—Halogenated unsaturated alcohols
  • C07C33/46—Halogenated unsaturated alcohols containing only six-membered aromatic rings as cyclic parts
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C35/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a ring other than a six-membered aromatic ring
  • C07C35/48—Halogenated derivatives
  • C07C35/52—Alcohols with a condensed ring system
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/02—Ethers
  • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
  • C07C43/23—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing hydroxy or O-metal groups
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C43/00—Ethers; Compounds having groups, groups or groups
  • C07C43/30—Compounds having groups
  • C07C43/315—Compounds having groups containing oxygen atoms singly bound to carbon atoms not being acetal carbon atoms
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
  • C07C49/76—Ketones containing a keto group bound to a six-membered aromatic ring
  • C07C49/84—Ketones containing a keto group bound to a six-membered aromatic ring containing ether groups, groups, groups, or groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/62—Halogen-containing esters
  • C07C69/63—Halogen-containing esters of saturated acids
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
  • C07C69/96—Esters of carbonic or haloformic acids
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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
  • C07D303/02—Compounds containing oxirane rings
  • C07D303/12—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms
  • C07D303/18—Compounds containing oxirane rings with hydrocarbon radicals, substituted by singly or doubly bound oxygen atoms by etherified hydroxyl radicals
  • C07D303/20—Ethers with hydroxy compounds containing no oxirane rings
  • C07D303/24—Ethers with hydroxy compounds containing no oxirane rings with polyhydroxy compounds
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  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
  • C07D303/02—Compounds containing oxirane rings
  • C07D303/48—Compounds containing oxirane rings with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms, e.g. ester or nitrile radicals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
  • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
  • C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D309/10—Oxygen atoms
  • C07D309/12—Oxygen atoms only hydrogen atoms and one oxygen atom directly attached to ring carbon atoms, e.g. tetrahydropyranyl ethers
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
  • C07D317/44—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems
  • C07D317/46—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 ortho- or peri-condensed with carbocyclic rings or ring systems condensed with one six-membered ring
  • C07D317/48—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring
  • C07D317/62—Methylenedioxybenzenes or hydrogenated methylenedioxybenzenes, unsubstituted on the hetero ring with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to atoms of the carbocyclic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
  • C07D317/72—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 spiro-condensed with carbocyclic rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
  • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
  • C07D319/14—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems
  • C07D319/16—1,4-Dioxanes; Hydrogenated 1,4-dioxanes condensed with carbocyclic rings or ring systems condensed with one six-membered ring
  • C07D319/18—Ethylenedioxybenzenes, not substituted on the hetero ring
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists

Definitions

• the present invention relates to compounds, compositions, methods for exerting a sensitizing effect, and manufacturing methods.
• Patent Document 1 discloses a resist composition that has a structure in which multiple aromatic rings are crosslinked and contains a compound that has an iodine atom. This resist composition has excellent etching resistance.
• Patent Document 2 discloses a compound that has a polymerizable group and an iodine atom. It is said that a resist composition that contains this compound can form a resist pattern with excellent CD uniformity.
• the present invention aims to provide a compound useful as a lithography composition, a composition containing the compound, a method for achieving a sensitizing effect using the compound, and a method for producing the compound.
• RG is a group containing at least one cyclic structure, I is an iodine atom, R 1 is a monovalent functional group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, which may be the same or different; n is an integer from 1 to 5; m is an integer from 1 to 5.
• a compound represented by the formula: [2] RG is a group derived from benzene, naphthalene, anthracene, pyrene, a heteroaromatic ring, or a polycyclic alicyclic ring which may have a substituent
• the R 1 is R f is selected from the group consisting of a hydroxyl group and an ether group having a protecting group; and a hydrocarbon group R g having 0 to 30 carbon atoms which may have a substituent;
• R f is R f ′ selected from the group consisting of one or more hydroxyl groups and ether groups having a protecting group which is removable by an acid, an alkali, or heat; The above compound.
• RG is a group derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorene, or adamantane, which may have a substituent; The above compound.
• RG is a group derived from benzene, naphthalene, or adamantane which may have a substituent; The above compound.
• R 1 is selected from -OR 2 , -COOR 3 , -CH 2 -OR 4 , or -CHO;
• R2 is a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, or an optionally substituted aryl group having 1 to 30 carbon atoms
• R3 is a hydrogen atom, an optionally substituted alkyl group having 1 to 29 carbon atoms, or an optionally substituted aryl group having 1 to 29 carbon atoms
• R 4 is a hydrogen atom, an optionally substituted alkyl group having 1 to 29 carbon atoms, or an optionally substituted aryl group having 1 to 29 carbon atoms; The above compound.
• I, A, and R1 are defined as above; R′′ is a hydrogen atom or an organic group other than R1 ; s1 is an integer from 1 to 7, s2 and s3 are an integer from 0 to 7, and s4 is an integer from 1 to 7. However, the sum of s1 to s4 is equal to or less than the valence of naphthalene, and at least one of s2 and s3 is selected to be 1 or more.
• I, R 1 and R′′ are defined as above; t1 is an integer from 1 to 10, t2 is an integer from 1 to 9, and t3 is an integer from 1 to 14.
• each R 1 does not include a combination of an alkoxy group (excluding those having a protecting group) and an aldehyde group, a combination of the alkoxy group and a hydroxyl group, or a combination of a hydroxyl group and an aldehyde group;
• the R 1 does not include a combination of a hydroxyl group and a carboxyl group.
• R 1' is a monovalent functional group, which may be the same or different, having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, excluding a hydroxyl group; r1', r2', and r4' are integers from 0 to 5, and the sum of r1', r2', and r4' is equal to or less than the valence of benzene.
• r1', r2', and r4' are integers from 0 to 5, and the sum of r1', r2', and r4' is equal to or less than the valence of benzene.
• A' is a group having a protecting group and is represented by -ORa - ORb , -O-CO- ORb , or -ORa -CO- ORb .
• R a is a linear or branched alkyl group having 1 to 3 carbon atoms.
• R b is a monovalent linear, branched or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group which forms a ring together with the adjacent oxygen atom.
• A' is a group having a protecting group and is represented by -ORa - ORb , -O-CO- ORb , or -ORa -CO- ORb .
• R a is a linear or branched alkyl group having 1 to 3 carbon atoms.
• R b is a monovalent linear, branched or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group which forms a ring together with the adjacent oxygen atom.
• Z' is I, R 1 or a hydrogen atom.
• R b is a monovalent linear, branched or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group which forms a ring together with the adjacent oxygen atom.
• the R 1 is a hydroxyl group, a carboxyl group, an ester group, or a hydroxyalkyl group; The above compound.
• RG is a group derived from adamantane which may have a substituent.
• the composition further comprises a compound represented by the following formula (DM0-1) or the following formula (BP0-1), or a combination thereof.
• DM0-1 a compound represented by the following formula (DM0-1) or the following formula (BP0-1), or a combination thereof.
• RG, I, and R1 are defined as in formula (1), Q is a group or a single bond resulting from a group connecting molecules, n' is an integer from 0 to 5 and not more than n; m' is an integer from 1 to 5 and not more than m; b is an integer from 1 to 4.
• Z is I, R 1 , or a linking group for forming a dimer; I and R1 are defined as in formula (1); A is a group having a protecting group, R is a non-functional organic group; R 1 , A and R are bonded to available positions; r1 to r4 are integers from 0 to 5, and the sum of r1 to r4 in one benzene is equal to or less than the valence of the benzene.
• R′′ is a hydrogen atom or an organic group other than R1 ; I, R 1 , A, and R′′ are bonded to available positions; Q is defined the same as in formula (DM0-1), s1 is an integer from 1 to 7, s2 and s3 are an integer from 0 to 7, and s4 is an integer from 1 to 7. However, the sum of s1 to s4 is equal to or less than the valence of naphthalene, and either s2 or s3 is selected to be 1 or more. nd is an integer from 1 to 4.
• R1 are defined the same as in formula (Dn1), R′′ is a hydrogen atom or an organic group other than R1 ; R d is a single bond or —O— (ether bond); t1 is an integer from 1 to 10, t2 is an integer from 1 to 9, and t3 is an integer from 1 to 13. However, the sum of t1 to t3 is equal to or less than the valence of adamantane.
• r1, r2, and r3 are integers from 0 to 5; a1 and r4a are integers from 0 to 4, a1 and r4a satisfy a1+r4a ⁇ r4, where r4 is defined the same as in formula (DM1a).
• s2 to s4 are defined the same as in formula (Dn1), s1b is an integer from 0 to 6, and satisfies s1b ⁇ (s1-1).
• s1 is defined the same as in formula (Dn1).
• composition wherein the compound represented by formula (BP0-1) is a compound represented by formula (BP1a) and Z is not I, a compound represented by formula (Bn1), or a compound represented by formula (Ba1).
• the composition wherein the compounds represented by formula (1), formula (DM0-1), and formula (BP0-1) satisfy the following relationship: 0.1 ⁇ ([total amount (mol) of the compound of formula (DM0-1) and the compound of formula (BP0-1)]) ⁇ [amount (mol) of the compound of formula (1)] ⁇ 0.000001 [39]
• the above composition, wherein the compound represented by formula (DM0-1) is a compound represented by the following formula (DM1a-Dt), (DM1a-Dt2), (Dn1-Dt), (Dn1-Dt2), (Da1-Dt), (Da1-Dt2), (Ba1-tl), (Ba1-x), or (Ba1-eb), and the compound represented by formula (BP0-1) is a compound represented by formula (DM1
• a method for producing the above compound comprising the step of introducing an iodine atom or an R1 group into the compound containing the RG group.
• a method for producing a compound represented by formula (1) comprising the steps of:
• the compound represented by formula (1) is represented by formula (Bz), (In the formula, I, Z, R 1 , A, R, and r1 to r4 are defined the same as in formula (DM1a).) 1) preparing a compound represented by formula (MB); (In the formula, I, R 1 , R, r1, and r2 are defined the same as in formula (Bz), and R 1 , R, and OH are bonded to any available position.) 2) an iodination step of iodizing the compound; 3) a protecting group introduction step of introducing a protecting group into the compound; and 4) a reduction step of reducing the compound.
• a method for producing the above compound comprising: [49] The method for producing the compound according to [48], wherein the protecting group introduction step comprises a step of introducing a protecting group into the hydroxy group of formula (MB) using an inorganic base.
• a method for producing a compound represented by formula (1) comprising the steps of:
• the compound represented by formula (1) is represented by formula (Bz), (In the formula, I, Z, R 1 , A, R, and r1 to r4 are defined the same as in formula (DM1a).) 1) preparing a compound represented by formula (Bz4); (In the formula, I, R, A, and Z are defined as in formula (Bz), R 1' may be the same or different and is a functional group having 0 to 30 carbon atoms and containing no polymerizable unsaturated bond, excluding a monovalent hydroxyl group; r1', r2', and r4' are integers from 0 to 5, and the sum of r1', r2', and
• a method for producing a compound represented by formula (1) comprising the steps of:
• the compound represented by formula (1) is represented by formula (Bz), (In the formula, I, Z, R 1 , A, R, and r1 to r4 are defined the same as in formula (DM1a).) 1) preparing a compound represented by formula (Bz5); (In the formula, I, Z, R 1 , A, R, and r1 to r4 are defined the same as in formula (DM1a).) 2) esterifying the carboxylic acid of the compound represented by formula (Bz5); 3) reducing the resulting ester group to convert it into a hydroxymethyl group; A method for producing the above compound, comprising: [52] A method for producing a compound represented by formula (1), comprising the steps of:
• the compound represented by formula (1) is represented by formula (N), (In the formula,
• s1 to s4 is equal to or less than the valence of naphthalene, and either s2 or s3 is selected to be 1 or more.
• a method for producing the above compound comprising: [53] A method for producing a compound represented by formula (1), comprising the steps of:
• the compound represented by formula (1) is represented by formula (Ad), (In the formula, I, R 1 and R′′ are defined as in formula (Da1), I, R 1 and R′′ are bonded to any available position; t1 is an integer from 1 to 10, t2 is an integer from 1 to 9, and t3 is an integer from 1 to 14. However, the sum of t1 to t3 is equal to or less than the valence of adamantane.
• a method for producing the above compound comprising: [54] The method for producing the compound according to any one of [48] to [53], wherein the iodination step includes a step of performing iodination in a multiphase system including an organic phase containing an organic solvent as a solvent and an aqueous phase containing water as a solvent.
• a method for producing the above compound comprising any one or more steps selected from the following: [58] 1) preparing a compound represented by formula (Ad-A-3-0); 2) an oxidation step of oxidizing a compound represented by formula (Ad-A-3-0); 3) esterifying the carboxylic acid of the obtained compound; 4) hydrolyzing the ester group of the resulting compound to convert it into a carboxylic acid; 5) an iodination step of iodizing the solution;
• a method for producing the compound according to [57], comprising: [59] The method according to any one of [47] to [58], further comprising a step of treating with an adsorbent.
• the present invention provides a compound useful as a composition for lithography, a composition containing the compound, a method for achieving a sensitizing effect using the compound, and a method for producing the compound. Furthermore, the compound and composition of the present invention can be used in a lithography process to obtain a sensitizing effect.
• RG is a group containing at least one cyclic structure.
• the valence of RG is appropriately adjusted depending on the number of substituents other than I, R 1 and R 1 described later.
• the group containing a cyclic structure may contain an aromatic ring, an alicyclic ring or a heterocyclic ring, but is preferably a group having 6 to 60 carbon atoms, and is more preferably a group derived from an aromatic ring, a heteroaromatic ring, such as benzene, naphthalene, biphenyl, anthracene, phenanthrene, pyrene, or fluorene, which may have a substituent, or a polycyclic alicyclic ring, such as cyclohexane, cyclododecane, dicyclopentane, tricyclodecane, or adamantane.
• RG may not contain a ring assembly in which a single ring is bonded by a single bond (e.g., biphenyl, binaphthyl, bicyclopropyl, etc.).
• RG is preferably a group having at least one cyclic structure selected from a monocyclic aromatic ring structure, a condensed ring aromatic structure, and a polycyclic alicyclic structure.
• RG is preferably a group derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorene, or a polycyclic alicyclic ring, which may have a substituent, more preferably a group derived from benzene, naphthalene, anthracene, pyrene, a heteroaromatic ring, or a polycyclic alicyclic ring, which may have a substituent, even more preferably a group derived from benzene, naphthalene, anthracene, phenanthrene, pyrene, fluorene, or adamantane, which may have a substituent, and particularly preferably a group derived from benzene, naphthalene, or adamantane.
• I is an iodine atom.
• n represents the number of I and is an integer of 1 to 5. From the viewpoints of the sensitizing effect, solubility in a solvent, and chemical stability, n is preferably an integer of 1 to 3, and more preferably 1 or 2. When n is greater than 1, a sensitizing effect can be obtained, and when n is 5 or less, the solubility of the compound in a solvent component commonly used for semiconductors and the stability of the compound itself can be ensured.
• R 1 may be the same or different and is a monovalent functional group having 0 to 30 carbon atoms and containing no polymerizable unsaturated bond. By converting R 1 to another group or bonding with another group, a derivative of the compound of formula (1) can be produced.
• the polymerizable unsaturated bond is an ethylenic double bond or triple bond.
• R 1 is a functional group, not an alkyl group.
• R 1 is, for example, an alkoxy group having 1 to 30 carbon atoms, a carboxyl group having 1 to 30 carbon atoms, a carboxylate group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, a hydroxyalkyl group having 1 to 30 carbon atoms, an aldehyde group, a halogen atom other than an iodine atom, a nitro group, an amino group, a thiol group, a cyano group, or a hydroxyl group.
• R 1 is preferably a hydroxyl group, a carboxyl group, an ester group, a hydroxyalkyl group, a halogen atom other than an iodine atom, a nitro group, an amino group, or a cyano group.
• groups that can have a substituent may have a substituent.
• substitution means that one or more hydrogen atoms in the functional group are substituted with a substituent.
• the "substituent” is not particularly limited, but examples thereof include halogen atoms, hydroxyl groups, cyano groups, nitro groups, thiol groups, heterocyclic groups, linear aliphatic hydrocarbon groups having 1 to 20 carbon atoms, branched aliphatic hydrocarbon groups having 3 to 20 carbon atoms, cyclic aliphatic hydrocarbon groups having 3 to 20 carbon atoms, aryl groups having 6 to 20 carbon atoms, alkoxyl groups having 1 to 20 carbon atoms, amino groups having 0 to 20 carbon atoms, alkenyl groups having 2 to 20 carbon atoms, alkynyl groups having 2 to 20 carbon atoms, acyl groups having 1 to 30 carbon atoms (preferably alkyloyloxy groups having 1 to 20 carbon atoms, aryloyloxy groups having 7 to 30 carbon atoms), alkoxycarbonyl groups having 2 to 20 carbon atoms, and alkylsilyl groups having 1 to 20 carbon atoms.
• These groups may form a ring structure within the substituent or a group having a substituent, or together with another R 1 .
• Preferred examples of the group which may form a ring structure include a glycidyl group, a cyclic acetal group, and a group in which two adjacent hydroxyl groups have an acetal protecting group structure.
• R 1 is preferably a hydroxyl group, a carboxyl group, an ester group, or a hydroxyalkyl group, and more preferably a group represented by -OR 2 , an alkoxy group having 1 to 30 carbon atoms, a hydroxyl group, a carboxyl group having 1 to 30 carbon atoms, a carboxylate group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, or an aldehyde group.
• R 2 is a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 1 to 30 carbon atoms, or a cyclic alkyl ether group having 1 to 5 carbon atoms.
• the carboxyl group or the carboxylate group is more preferably represented by -COOR 3.
• R 3 is a hydrogen atom, an alkyl group having 1 to 29 carbon atoms, or an aryl group having 1 to 29 carbon atoms.
• the alkoxyalkyl group or the hydroxyalkyl group is more preferably represented by -CH 2 -OR 4 .
• R4 is a hydrogen atom, an alkyl group having 1 to 29 carbon atoms, or an aryl group having 1 to 29 carbon atoms.
• the alkyl group or aryl group may have a substituent.
• An example of the substituent is an alkoxy group.
• R2 in -OR2 can be -CH2- OC2H5 .
• the alkyl group in R 2 to R 4 is preferably a methyl group, an ethyl group, or a propyl group (including isomers; the same applies below).
• the aryl group is preferably a phenyl group or a naphthyl group.
• R 1 may have a protecting group.
• a protecting group is a group that dissociates under specific conditions, and is also called a dissociable group.
• the protecting group is preferably an acid-dissociable group that dissociates in the presence of an acid.
• Preferred examples of the group include a 1-substituted ethyl group, a 1-substituted n-propyl group, a 1-branched alkyl group, a silyl group, an acyl group, a 1-substituted alkoxymethyl group, a cyclic ether group, an alkoxycarbonyl group, or an alkoxycarbonylalkyl group.
• R 1 may be a hydroxyl group or a carboxyl group protected by a protecting group.
• R 1 is -O-CH 2 -O-R'.
• R' is, for example, an alkyl group having 1 to 5 carbon atoms. This embodiment corresponds to the case where R 1 is -OR 2 (wherein R 2 is CH 3 ) and R 2 has an alkoxy group (-O-R') as a substituent.
• R 1 may be represented as A or A' as described below.
• m represents the number of R 1 and is an integer of 1 to 5. From the viewpoint of solubility in a solvent, m is preferably 4, 3, 2, or 1. When m is 2 or 3, the multiple R 1s may be different or the same. m is more preferably 2 or 3, and even more preferably 2. The total number of m and n is appropriately adjusted depending on the valence of RG.
• the compound may have an organic group other than R1 as a substituent, if necessary.
• An example of the organic group is an alkyl group having 1 to 30 carbon atoms. A plurality of such groups may be present. However, it is preferable that the compound does not contain any organic group other than R1 and an iodine atom.
• the R 1 does not include a combination of an alkoxy group and an aldehyde group, an alkoxy group and a hydroxyl group, or an aldehyde group and a hydroxyl group.
• the alkoxy group here does not include those having a protecting group.
• the alkoxy group is, for example, a methoxy group or an ethoxy group.
• the R 1 does not include a combination of a hydroxyl group and a carboxyl group.
• R 1 is preferably one selected from one or more R f and zero or more R g .
• R 1 is also one selected from one or more R f ' and zero or more R g .
• R f is selected from the group consisting of a hydroxyl group and an ether group having a protecting group.
• R f ' is selected from the group consisting of a hydroxyl group and an ether group having a protecting group that is released by an acid, an alkali, or heat.
• R g is a hydrocarbon group having 0 to 30 carbon atoms which may have a substituent.
• R 1 is preferably one selected from R f selected from the group consisting of one or more hydroxyl groups and ether groups having a protecting group, and zero or more hydrocarbon groups R g having 0 to 30 carbon atoms and which may have a substituent
• R f is more preferably R f ' selected from the group consisting of one or more hydroxyl groups and ether groups having a protecting group which is eliminated by an acid, an alkali, or heat.
• the compound of formula (1) can be linked to other compounds.
• the compound of formula (1) can be a dimer to a pentamer. Multimers will be described later.
• RG is benzene.
• the compound represented by formula (1) (hereinafter referred to as "compound of formula (1)” or the like) is preferably represented by formula (Bz) from the viewpoints of sensitizing effect, easy availability, and the like.
• A is a group having a protecting group.
• A becomes a functional group by removing the protecting group, and is therefore a type of R1 .
• the protecting group is preferably an acid-dissociable group. Therefore, the group having a protecting group is preferably a group in which a hydroxyl group or a carboxyl group is protected with an acid-dissociable group.
• A can be A' represented by -O-R a -O-R b , and in this case, it is preferable that the compound of formula (Bz) contains one or more of said A'.
• R a and R b will be described later.
• R is an organic group that is not a functional group.
• the organic group can be an alkyl group having 1 to 30 carbon atoms.
• Z is I, R 1 , or a linking group for forming a dimer.
• Z is a linking group for forming a dimer, two molecules are bonded by a single bond to generate a dimer.
• the dimer is included in the compound represented by formula (DM1a) described later.
• Z may not include a linking group for forming a dimer.
• Z is particularly represented as Z'.
• R1 is preferably a hydroxyl group, a carboxyl group, an ester group, a hydroxyalkyl group, a halogen atom other than an iodine atom, a nitro group, an amino group, or a cyano group.
• R 1 , R, and A are bonded to any possible positions.
• r1 to r4 are integers of 0 to 5, and the sum of r1 to r4 is equal to or less than the valence of benzene.
• r1 to r4 are preferably integers of 1 to 4, more preferably integers of 1 to 3, and particularly preferably an integer of 1 or 2.
• the compound of formula (Bz) is preferably represented by formula (Bz1).
• the compound of formula (Bz1) has one R 1 that is not derived from Z.
• each substituent of the compound is defined in the same way as the compound group to which the compound belongs.
• the compound of formula (Bz1) is preferably represented by formula (Bz1-1).
• the compound of formula (Bz1-1) has one R 1 not derived from Z at the meta position of I.
• the compound of formula (Bz1-1) is preferably represented by formula (1b), more preferably by formula (1b-3).
• Z' may be I, R 1 or a hydrogen atom, and A and Z, or A and Z' may form a cyclic structure together with a protecting group.
• the compound of formula (Bz1-1) is preferably represented by formula (1b-1), and more preferably represented by formula (1b-4).
• the compound of formula (Bz1) is preferably represented by formula (Bz1-2).
• the compound of formula (Bz1-2) has one R1 not derived from Z at the para position of I.
• a and Z may form a cyclic structure together with a protecting group.
• Z and R1 may form a cyclic structure together with a protecting group.
• I, R, Z, and R1' are defined the same as in formula (Bz4).
• r1', r2', and r4' are integers from 0 to 5, and the sum of r1', r2', and r4' is equal to or less than the valence of benzene.
• the compound of formula (Bz4-1) is particularly preferably represented by formula (Bz4-2). This compound has a hydroxymethyl group and an iodine atom.
• I is defined the same as in formula (Bz4), r4' is an integer from 0 to 4, and r5' is an integer from 0 to 4. From the viewpoint of the effect of improving the resist sensitivity, r4' is preferably an integer from 1 to 4, and more preferably an integer from 1 to 3. r5' is preferably an integer from 0 to 3, and more preferably an integer from 0 to 2.
• RG is naphthalene.
• the compound is preferably represented by formula (N) from the viewpoints of sensitizing effect, availability, and the like.
• R 1 is a monovalent functional group having 0 to 30 carbon atoms, which may be the same or different, and does not contain a polymerizable unsaturated bond.
• R 1 is defined as in the first embodiment, but from the viewpoint of sensitization effect, etc., R 1 is preferably a hydroxyl group, a carboxyl group, an ester group, or a hydroxyalkyl group.
• A is a group having a protecting group.
• A can be A' represented by -O-R a -O-R b , and in this case, it is preferable that the compound of formula (N) contains one or more A's.
• R" is a hydrogen atom or an organic group other than R 1.
• s1 is preferably an integer of 1 to 7, more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3.
• s2 and s3 are preferably integers of 0 to 7, more preferably integers of 0 to 5, and particularly preferably 1 to 3.
• s4 is preferably an integer of 1 to 7, and more preferably an integer of 1 to 6.
• s4 is a number that satisfies s4 ⁇ 8 ⁇ s1 ⁇ s2 ⁇ s3.
• the sum of s1 to s4 is equal to or less than the valence of naphthalene.
• at least one of s2 and s3 is 1 or more.
• the compound in which RG is naphthalene may have a linking group Z for forming a dimer.
• the compound is represented by formula (N').
• each substituent is defined as above, and the bonding position is also arbitrary.
• s1 is preferably an integer of 1 to 7, more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3.
• s2 and s3 are preferably integers of 0 to 7, more preferably integers of 0 to 5, and particularly preferably 1 to 3.
• s4 is preferably an integer of 1 to 7, and more preferably an integer of 1 to 6.
• s5 is preferably an integer of 1 to 2. However, the sum of s1 to s5 is equal to or less than the valence of naphthalene, and at least one of s2 and s3 is 1 or greater.
• the compound of formula (N) is preferably represented by formula (n), formula (2n) or formula (3n).
• I, R 1 , A and R′′ are defined the same as in formula (N).
• x and y are 0 or 1, provided that at least one of them is 1.
• s4′ represents the number of R′′ that can be bonded to the 1st, 7th and 8th positions of naphthalene (where the carbon at the top of the right ring is considered to be the 1st position, and the same applies below), and is an integer from 1 to 3.
• the compound of formula (n) is preferably represented by formula (1n), more preferably (1n-1). As described above, when there are a plurality of R 1 , the R 1 does not include a combination of a hydroxyl group and a carboxyl group.
• the compound of formula (n) is preferably represented by formula (1n'), more preferably represented by formula (1n'-1). As described above, when there are a plurality of R 1 , the R 1 does not include a combination of a hydroxyl group and a carboxyl group.
• the compound of formula (2n) is preferably represented by formula (2n-1), more preferably (2n-1-1). As described above, when there are a plurality of R 1 , the R 1 does not include a combination of a hydroxyl group and a carboxyl group.
• the compound of formula (3n) is preferably represented by formula (3n-1), more preferably (3n-1-1). As described above, when there are a plurality of R 1 , the R 1 does not include a combination of a hydroxyl group and a carboxyl group.
• the compound of formula (3n) is preferably represented by formula (3n-2), and more preferably represented by formula (3n-2-1). As described above, when there are a plurality of R 1 , the R 1 does not include a combination of a hydroxyl group and a carboxyl group.
• R c is a monovalent group having 0 to 29 carbon atoms and containing no polymerizable unsaturated bonds.
• A is a group having a protecting group.
• A is, for example, but not limited to, the following:
• RG is an alicyclic ring having a polycyclic structure with 3 to 30 carbon atoms. Substituents such as I and R1 in the alicyclic ring may be present at any position. Specific examples of the alicyclic ring include the following structures. These alicyclic rings may further have an alicyclic structure.
• RG is adamantane. Therefore, in this embodiment, the compound of formula (1) is preferably represented by formula (Ad).
• I, R 1 and R" are defined as above. However, I, R 1 and R" are bonded to any position of the adamantane.
• the protecting group is preferably an acid-dissociable group as described above. Therefore, the group having a protecting group is preferably a group in which a hydroxyl group or a carboxyl group is protected with an acid-dissociable group.
• R 1 is preferably a hydroxyl group, a carboxyl group, an ester group, or a hydroxyalkyl group from the viewpoint of sensitization effect and the like.
• R 1 can be A, or may be A' represented by -O-R a -O-R b .
• the compound of formula (Ad) contains 1 or more A.
• t1 is preferably an integer of 1 to 10, more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3.
• t2 is preferably an integer of 1 to 9, more preferably an integer of 1 to 5, and particularly preferably an integer of 1 to 3.
• t3 is preferably an integer of 1 to 14, more preferably an integer of 5 to 14, and particularly preferably an integer of 8 to 14.
• t3 is a number that satisfies t3 ⁇ 16 ⁇ t1 ⁇ t2.
• t1 to t3 is equal to or less than the valence of adamantane.
• preferred compounds will be described from the viewpoints of sensitizing effect, availability, and the like. Note that the compound in which RG is adamantane may have a linking group Z at any position for forming a dimer.
• the compound of formula (Ad) is preferably represented by formula (Ad1): In one embodiment, one of D is I and the other of D is R1 . In another embodiment, both D are R1 .
• the compound of formula (Ad) is preferably represented by formula (1a), (2a), or (3a).
• the compound of formula (Ad1) is preferably represented by the following formula:
• the organic group is as described in the first or second aspect.
• the compound has 1 to 2 iodine atoms.
• R 1 is preferably a hydroxyl group, a carboxyl group, an ester group (which may have a substituent other than iodine atom such as a halogen atom), or a hydroxyalkyl group.
• the compound of formula (1) may be a polymer.
• RG does not include a ring assembly in which single rings are bonded by a single bond (e.g., biphenyl, binaphthyl, bicyclopropyl, etc.).
• RG is a group having at least one ring structure selected from a monocyclic aromatic ring structure, a condensed ring aromatic structure, and a polycyclic alicyclic structure.
• at least a part of R 1 is preferably the following group, and connects two or more molecules.
• the carbonate group may be an alkoxycarbonyloxy group or an aryloxycarbonyloxy group, which may have a substituent.
• the compound of formula (1) is a polymer
• the compound is preferably represented by the following formula:
• RG, I, and R 1 are defined the same as in formula (1).
• n' is an integer of 0 to 5 and not more than n, and is preferably an integer of 1 to 3.
• m' is an integer of 1 to 5 and not more than m, and is preferably an integer of 1 to 4.
• b is an integer of 1 to 4, preferably an integer of 1 to 3, and more preferably an integer of 1 or 2.
• Q is a single bond or a group resulting from R 1 bonding between molecules. When Q is resulting from Z, Q is a single bond, which means that the repeating units are bonded by a single bond. When Q is resulting from R 1 bonding between molecules, Q is, for example, an ester group, etc.
• R, R 1 , A, Z, r1 to r4 are defined as in the compounds of the formula (Bz) family.
• Z is preferably R 1 .
• the compound of formula (DM1a) is preferably a compound represented by formula (DM1b).
• the compound represented by formula (DM1b) is preferably a compound represented by formula (DM1c1).
• the compound represented by formula (DM1c1) is preferably a compound represented by formula (DM1d11).
• the compound represented by formula (DM1c1) is preferably a compound represented by formula (DM1d12).
• A' is a group having a protecting group, and is represented by -O-R a -O-R b , -O-CO-O-R b , or -O-R a -CO-O-R b , or by -O-R a -O-CO-R b .
• R a is a linear or branched alkyl group having 1 to 3 carbon atoms.
• R b is a monovalent linear or branched alkyl group or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group, which forms a ring together with the adjacent oxygen atom.
• a cyclic structure including R a and R b may be formed. However, there is at least one A'.
• the compound represented by formula (DM1b) is preferably a compound represented by formula (DM1c2).
• the compound represented by formula (DM1c2) is preferably a compound represented by formula (DM1d21) below.
• the compound represented by formula (DM1c1) is preferably a compound represented by formula (DM1d22).
• the compound represented by formula (DM1b) is preferably a compound represented by formula (DM1c3).
• the compound represented by formula (DM1c3) is preferably a compound represented by formula (DM1d31).
• the compound represented by formula (DM1b) is preferably a compound represented by formula (DM1c4).
• the compound represented by formula (DM1c4) is preferably a compound represented by formula (DM1d41).
• the compound of formula (DM1a) is preferably a compound represented by formula (DM1e).
• I, R, A, and Z are defined as in formula (DM1a), and R 1 ' , r1 ', r2 ', and r4 ' are defined as in formula (Bz4).
• the compound of formula (DM1e) is preferably a compound represented by formula (DM1e1).
• the compound of formula (DM1e1) is preferably a compound represented by formula (DM1e2).
• dimer compound An example of a dimer compound is shown below.
• I, R, R 1 and A are defined as in formula (Bz).
• This compound corresponds to the compound of formula (1b) in which Z is a linking group for forming a dimer.
• nd is an integer of 1 to 4, and preferably an integer of 1 to 2.
• Q is a single bond, and nd is preferably 1.
• the compound represented by formula (Dn1) is preferably a compound represented by formula (Dn1a).
• I, R 1 , R′′, A, and nd are defined the same as in formula (Dn1).
• x and y are each 0 or 1, and at least one of x and y is 1.
• s4′ represents the number of R′′ bonded to positions 1, 7, and 8 of naphthalene.
• the compound represented by formula (Dn1a) is preferably a compound represented by formula (Dn1b1).
• the compound represented by formula (Dn1b1) is preferably a compound represented by formula (Dn1c11).
• I, R 1 , R′′, A, and nd are defined the same as in formula (Dn1); x and y are each 0 or 1, and at least one of x and y is 1. nd is preferably 2.
• the compound represented by formula (Dn1b1) is preferably a compound represented by formula (Dn1c12).
• A′ is a group having a protecting group and is represented by —O—R a —O—R b , —O—CO—O—R b , or —O—R a —CO—O—R b .
• nd is preferably 2.
• the compound represented by formula (Dn1a) is preferably a compound represented by formula (Dn1b2).
• the compound represented by formula (Dn1b2) is preferably a compound represented by formula (Dn1c21).
• R 1 , R", A, and nd are defined the same as in formula (Dn1), and Z is defined the same as in formula (DM1a).
• A' is a group having a protecting group and is represented by -O-R a -O-R b , -O-CO-O-R b , or -O-R a -CO-O-R b .
• R a is a linear or branched alkyl group having 1 to 3 carbon atoms.
• R b is a monovalent linear, branched alkyl group or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group which forms a ring together with the adjacent oxygen atom.
• nd is preferably 2.
• the compound represented by formula (Dn1a) is preferably a compound represented by formula (Dn1b3).
• the compound represented by formula (Dn1b3) is preferably a compound represented by formula (Dn1c31).
• R 1 , R", and nd are defined the same as in formula (Dn1), and Z is defined the same as in formula (DM1a).
• A' is a group having a protecting group and is represented by -O-R a -O-R b , -O-CO-O-R b , or -O-R a -CO-O-R b .
• R a is a linear or branched alkyl group having 1 to 3 carbon atoms.
• R b is a monovalent linear, branched alkyl group or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group which forms a ring together with the adjacent oxygen atom.
• nd is preferably 2.
• the compound represented by formula (Dn1b3) is preferably a compound represented by formula (Dn1c32).
• R 1 , R", and nd are defined the same as in formula (Dn1), and Z is defined the same as in formula (DM1a).
• A' is a group having a protecting group and is represented by -O-R a -O-R b , -O-CO-O-R b , or -O-R a -CO-O-R b .
• R a is a linear or branched alkyl group having 1 to 3 carbon atoms.
• R b is a monovalent linear, branched alkyl group or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group which forms a ring together with the adjacent oxygen atom.
• nd is preferably 2.
• Non-limiting specific examples of formula (Dn1) are shown below.
• the compound of formula (DM0-1) is represented by formula (Da1).
• the compound of formula (Da1) is more preferably represented by formula (Da2).
• the compound represented by formula (Da1) is preferably a compound represented by formula (Da1a).
• the compound represented by formula (Da1a) is preferably a compound represented by formula (Da1b).
• the compound of formula (DM0-1) is represented by formula (Da1c11).
• the compound represented by formula (Da1b) is preferably a compound represented by formula (Da1c12).
• the compound can be manufactured by any method as long as the effect is not impaired.
• a manufacturing method including a step of introducing an iodine atom or an R 1 group into a compound containing an RG group is preferred.
• the step of introducing an iodine atom into a compound having an aromatic ring can be carried out by reacting the compound having an aromatic ring with iodine I 2 under acid or alkaline conditions. This reaction can produce compounds and dimers with different numbers of iodine atoms. The production ratio of these is adjusted by the reaction conditions. In particular, lowering the reaction temperature or shortening the reaction time tends to increase the number of compounds with fewer iodine atoms and decrease the number of dimers.
• the step of introducing an iodine atom into a compound having an alicyclic ring can be carried out by reacting the compound having an alicyclic ring with HI (hydrogen iodide).
• a preferred method for producing the compound can include an iodination step of introducing an iodine atom, via a substitution reaction, into a raw material containing RG, a functional group capable of replacing an iodine atom via a substitution reaction, and, if necessary, R 1.
• Another method for producing the compound can include an iodination step of introducing iodine, either in the form of a radical or as a cation or anion, into a raw material containing RG and, if necessary, R 1 .
• the iodination step can be appropriately selected from a method of introducing a halogen from an amino group by the Sandmeyer reaction or the like, a method of reacting iodine chloride in an organic solvent (e.g., JP 2012-180326 A, JP 2000-256231 A, JP 2010-159233 A, J. Chem. Soc. 636, 1943), a method of adding iodine dropwise to an alkaline aqueous solution of phenol in the presence of ⁇ -cyclodextrin under alkaline conditions (JP 63-101342 A, JP 2003-64012 A), and the like.
• a method of introducing a halogen from an amino group by the Sandmeyer reaction or the like e.g., JP 2012-180326 A, JP 2000-256231 A, JP 2010-159233 A, J. Chem. Soc. 636, 1943
• the iodinating agent is not particularly limited, but examples thereof include iodine chloride, iodine, N-iodosuccinimide, iodic acid, and hydrogen iodide (including hydroiodic acid and aqueous hydrogen iodide solutions).
• the ratio of the iodinating agent to the substrate is preferably 1.2 molar times or more, more preferably 1.5 molar times or more, and even more preferably 2.0 molar times or more.
• the iodination reaction can proceed by reacting at least an iodinating agent with a substrate, and the target compound can be obtained under known iodine introduction reaction conditions using methods described in, for example, Adv. Synth. Catal. 2007, 349, 1159-1172, Organic Letters; Vol. 6; (2004); p. 2785-2788, and non-patent literature such as "Organic Synthesis Reagents and Synthesis Methods for Bromine and Iodine Compounds" (edited by Suzuki Hitomi, written by Manac Corporation Research Institute, Maruzen Publishing), and patent literature such as US5300506, US5434154, US2009/281114, EP1439164, and WO2006/101318.
• iodination agents examples include, but are not limited to, iodine compounds, monochloride iodide, N-iodosuccinimide, benzyltrimethylammonium dichloroiodate, tetraethylammonium iodide, tetra-normal-butylammonium iodide, lithium iodide, sodium iodide, potassium iodide, 1-chloro-2-iodoethane, silver iodine fluoride, tert-butyl hypoiodide, 1,3-diiodo-5,5-dimethylhydantoin, iodine-morpholine complex, trifluoroacetyl hypoiodide, iodine-iodic acid, iodine-periodic acid, iodine-hydrogen peroxide, 1-iodoheptafluoropropane,
• additives can be added to the iodination reaction to promote the reaction or suppress by-products.
• additives include acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, p-toluenesulfonic acid, ferric chloride, aluminum chloride, copper chloride, antimony pentachloride, silver sulfate, silver nitrate, and silver trifluoroacetate; bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate, and potassium bicarbonate; oxidizing agents such as cerium (IV) ammonium nitrate and sodium peroxodisulfate; inorganic compounds such as sodium chloride, potassium chloride, mercury (II) oxide, and cerium oxide; organic compounds such as acetic anhydride; and porous substances such as zeolites.
• acids such as hydrochloric acid, sulfuric acid, nitric acid,
• the ratio of additive to iodinating agent is preferably 1.0 molar amount, more preferably 1.2 molar amount or more, even more preferably 1.5 molar amount or more, and even more preferably 2.0 molar amount or more.
• iodine is preferably introduced into the mother nucleus using at least an iodine source and an oxidizing agent.
• an iodine source and an oxidizing agent is preferable in terms of reaction efficiency and purity improvement.
• the iodination source include the above-mentioned iodinating agents.
• the oxidizing agent include iodic acid, periodic acid, hydrogen peroxide, and other additives (hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, silver trifluoroacetate, cerium (IV) ammonium nitrate (CAN), etc.).
• the iodination reaction can be carried out using an iodine source such as iodine and a silver salt or fuming sulfuric acid to form an iodine cation species.
• an iodine source such as iodine and a silver salt or fuming sulfuric acid
• the iodination reaction can be carried out by forming hypoiodous acid and an iodine cation species by combining an iodine source with an inorganic salt.
• an inorganic salt potassium peroxodisulfate and the like can be used as appropriate.
• a method of introducing iodine into an aliphatic alcohol group by a substitution reaction can also be used as appropriate.
• iodinating agents hydrogen halides, phosphorus halides, sulfonyl halides (combination of NaI/acetone), thionyl halides, trimethylsilane halides, Vilsmeier reagents, and Abbel reaction (combination of triphenylphosphine and an iodine source) can be used as appropriate.
• reaction in the iodination step can be carried out neat, without a solvent, but examples of reaction solvents that can be used include halogen-based solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride; alkyl-based solvents such as hexane, cyclohexane, heptane, pentane, and octane; aromatic hydrocarbon-based solvents such as benzene and toluene; alcohol solvents such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, and 2-butanol; ether-based solvents such as diethyl ether, diisopropyl ether, and tetrahydrofuran; acetic acid, dimethylformamide, dimethyl sulfoxide, and water.
• reaction solvents include halogen-based solvents such as dichloromethane, dichloroethane, chloroform, and
• the reaction temperature of the iodination step is not particularly limited and may be any temperature between the freezing point and the boiling point of the solvent used in the reaction, but is preferably 0°C to 150°C, more preferably 20°C to 150°C, and even more preferably 50°C to 120°C.
• the reaction time of the iodination step is not particularly limited, but is preferably 0.25 to 48 hours, more preferably 0.25 to 24 hours, and even more preferably 1 to 12 hours.
• the reaction system may be refluxed in order to proceed with iodination more efficiently.
• a reflux tube equipped with a Dean-Stark or the like may be used to control the concentration of the iodinating agent in the reaction solution.
• the iodine substitution reaction in the iodination step can proceed by reacting at least an iodinating agent with a substrate.
• the target compound can be obtained under known iodine substitution reaction conditions, such as the Sandmeyer reaction using the method described in Chemistry - A European Journal, 24(55), 14622-14626; 2018, Synthesis (2007)(1), 81-84, etc.
• the protective group represented by A' can be introduced into RG by a known method, for example, a method appropriately selected from those described in Green's Protective Groups in Organic Synthesis (Peter GM Wuts, WILEY), p. 17 to p. 553.
• the ratio of the protecting group introduction agent to the substrate in the protecting group introduction step is not particularly limited, but is preferably 0.5 molar times or more, more preferably 1.0 molar times or more, and even more preferably 1.5 molar times or more.
• the reaction temperature in the protecting group introduction step is not particularly limited, but generally, a temperature of 0°C to 200°C is suitable, and from the viewpoint of yield, a temperature of 10°C to 190°C is preferable, a temperature of 25°C to 150°C is more preferable, and a temperature of 50°C to 100°C is even more preferable. In the reaction in this embodiment, the preferred temperature range is 0°C to 100°C.
• the reaction time in the protecting group introduction step is not particularly limited, but is preferably 0.25 to 48 hours, more preferably 0.25 to 24 hours, and even more preferably 1 to 12 hours.
• R 1 when R 1 is a hydroxyalkyl group or an aldehyde group, it can be obtained, for example, by introducing a carboxyl group, an ester group or an aldehyde group as R 1 and then reducing it.
• the reduction method may be a known method, such as a method using a metal hydrogen complex compound such as sodium borohydride, lithium aluminum hydride, sodium bis(2-methoxyethoxy)aluminum hydride (SBMEA), or diisobutylaluminum hydride (DIBAL), a method using a metal hydride such as aluminum hydride, or a method using these reducing agents together with a reduction assistant such as aluminum chloride or ethanedithiol.
• the reducing agent may be modified in part of its structure to an alkoxy group or a hydrocarbon group, or may be used in combination with Lewis acids to adjust the reducing ability.
• the reaction temperature may be at room temperature or under heated conditions, or may be cooled to adjust the reactivity. There are no particular limitations on the reaction temperature, but it is preferably -20°C to 150°C, more preferably 0°C to 150°C, and even more preferably 20°C to 120°C.
• the ratio of the reducing agent to the substrate in the reduction step is not particularly limited, but is preferably 0.5 molar or more, more preferably 1.0 molar or more, and even more preferably 1.5 molar or more.
• the reaction time in the reduction step is not particularly limited, but is preferably 0.25 to 48 hours, more preferably 0.25 to 24 hours, and even more preferably 1 to 12 hours.
• metal impurities can originate from reaction aids in the compound manufacturing process, or from the reaction kettle and other manufacturing equipment used in manufacturing.
• the residual amount of the above-mentioned metal impurities is preferably less than 1 ppm relative to the compound, more preferably less than 100 ppb, even more preferably less than 50 ppb, even more preferably less than 10 ppb, and most preferably less than 1 ppb.
• metal species classified as transition metals such as Fe, Ni, Sn, Zn, Cu, Sb, W, and Al
• the residual metal amount is 1 ppm or more, there is a concern that it may cause denaturation or deterioration of the material over time due to interactions with other compounds.
• the residual metal amount is 1 ppm or more, it is not possible to sufficiently reduce the residual metal amount when using the compound to produce resin for semiconductor processes, which may cause defects due to residual metals in the semiconductor manufacturing process and a decrease in yield due to performance deterioration, and there is a concern that the doping effect of the metal elements on the substrate may cause a decrease in characteristics.
• the purification method is not particularly limited, but may be the method described in WO 2015/080240 or the method described in WO 2018/159707.
• the purification method includes a step of dissolving the compound in an organic solvent that is not miscible with water to obtain an organic phase, contacting the organic phase with an acidic aqueous solution to perform an extraction process, thereby transferring the metal content contained in the organic phase containing the compound and the organic solvent to the aqueous phase, and then separating the organic phase from the aqueous phase.
• the organic solvent that is not miscible with water is usually an organic solvent classified as a non-water-soluble solvent.
• the organic solvent is not particularly limited, but is preferably an organic solvent that can be safely applied to the semiconductor manufacturing process.
• the amount of the organic solvent used is usually about 10% by mass relative to the compound used.
• organic solvents examples include those described in International Publication WO 2015/080240.
• toluene, 2-heptanone, cyclohexanone, cyclopentanone, methyl isobutyl ketone, propylene glycol monomethyl ether acetate (PGMEA), ethyl acetate, etc. are preferred, with cyclohexanone and propylene glycol monomethyl ether acetate being particularly preferred.
• the acidic aqueous solution is appropriately selected from among aqueous solutions in which a commonly known organic or inorganic compound is dissolved in water.
• aqueous solutions in which a commonly known organic or inorganic compound is dissolved in water.
• these acidic aqueous solutions can be used alone or in combination of two or more.
• the acidic aqueous solution include mineral acid aqueous solutions and organic acid aqueous solutions.
• the mineral acid aqueous solution include an aqueous solution containing one or more acids selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid.
• the organic acid aqueous solution examples include an aqueous solution containing one or more acids selected from the group consisting of acetic acid, propionic acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, tartaric acid, citric acid, methanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and trifluoroacetic acid.
• the pH range of the acidic aqueous solution is about 0 to 5, and more preferably about pH 0 to 3.
• Other production methods include the method using a filter described below, the method using an adsorptive ion exchange resin, passing the liquid through a column, dispersing and suspending the ion exchange resin in a container, and distillation methods, etc., which can be used as appropriate.
• the order and number of the iodination step, the protective group introduction step, and the reduction step are not particularly limited, and can be appropriately selected depending on the structure of the target compound.
• the filter used to remove metals from the solution containing the compound and the solvent can be one that is commercially available for liquid filtration.
• the filtration accuracy of the filter is not particularly limited, but the nominal pore size of the filter is preferably 0.2 ⁇ m or less, more preferably less than 0.2 ⁇ m, even more preferably less than 0.1 ⁇ m, and even more preferably less than 0.1 ⁇ m, and even more preferably 0.05 ⁇ m or less.
• the lower limit of the nominal pore size of the filter is not particularly limited, but is usually 0.005 ⁇ m.
• the nominal pore size here is a nominal pore size that indicates the separation performance of the filter, and is determined by a test method determined by the filter manufacturer, such as a bubble point test, a mercury porosimetry test, or a standard particle supplement test. When a commercially available product is used, it is the value described in the catalog data of the manufacturer.
• the nominal pore size 0.2 ⁇ m or less, the content of metals after passing the solution through the filter once can be effectively reduced.
• the filter passing step may be carried out two or more times.
• the filter may be in the form of a hollow fiber membrane filter, a membrane filter, a pleated membrane filter, or a filter filled with a filter medium such as nonwoven fabric, cellulose, or diatomaceous earth.
• the filter is one or more types selected from the group consisting of hollow fiber membrane filters, membrane filters, and pleated membrane filters.
• the filter material may be polyolefins such as polyethylene and polypropylene, polyethylene-based resins provided with functional groups having ion exchange capacity by graft polymerization, polar group-containing resins such as polyamide, polyester, and polyacrylonitrile, and fluorine-containing resins such as fluorinated polyethylene (PTFE).
• PTFE fluorinated polyethylene
• the filter medium is one or more selected from the group consisting of polyamide, polyolefin resin, and fluororesin.
• polyamide is particularly preferable from the viewpoint of the effect of reducing heavy metals such as chromium. It is preferable to use a filter material other than sintered metal from the viewpoint of avoiding metal elution from the filter medium.
• polyamide-based filters examples include, but are not limited to, the Polyfix nylon series manufactured by Kitz Microfilter Co., Ltd., Ultipleats P-nylon 66 and Ultipore N66 manufactured by Nippon Pole Co., Ltd., and the LifeAsure PSN series and LifeAsure EF series manufactured by 3M Limited.
• polyolefin filters include, but are not limited to, Ultipleats PE Clean and Ion Clean, both manufactured by Nippon Pole Co., Ltd., and Protego Series, Microguard Plus HC10, and Optimizer D, both manufactured by Nippon Entegris Co., Ltd.
• polyester-based filters include, but are not limited to, Gelaflow DFE manufactured by Central Filter Kogyo Co., Ltd. and Breeze Type PMC manufactured by Nippon Filter Co., Ltd.
• polyacrylonitrile filters include, but are not limited to, Ultrafilters AIP-0013D, ACP-0013D, and ACP-0053D manufactured by Advantec Toyo Co., Ltd.
• fluororesin filters include, but are not limited to, Enflon HTPFR manufactured by Nippon Pole Co., Ltd., and Lifesure FA series manufactured by 3M Limited. These filters may be used alone or in combination of two or more kinds.
• the filter may also contain an ion exchanger such as a cation exchange resin, or a cationic charge regulator that generates a zeta potential in the organic solvent solution to be filtered.
• an ion exchanger such as a cation exchange resin, or a cationic charge regulator that generates a zeta potential in the organic solvent solution to be filtered.
• filters containing an ion exchanger include, but are not limited to, the Protego series manufactured by Nippon Entegris Co., Ltd. and Clangraft manufactured by Kurashiki Sen-i Kako Co., Ltd.
• filters containing a substance having a positive zeta potential include, but are not limited to, Zeta Plus 40QSH (registered trademark) and Zeta Plus 020GN (registered trademark) manufactured by 3M Limited, and the Life Asure EF (registered trademark) series.
• ion exchange resin Other purification methods include treating a solution containing the compound with an ion exchange resin.
• an ion exchange resin a known ion exchange resin having a function corresponding to the target metal element can be appropriately used.
• Purification using an ion exchange resin is a process in which an ion exchange method or ion adsorption by a chelating group is performed on a product to be purified that contains the compound.
• Components removed by the treatment process using an ion exchange resin include, but are not limited to, acid components and metal ions contained in metal components.
• the method for carrying out the ion exchange method is not particularly limited, and known methods can be used.
• a typical example is a method in which a solution containing the compound is passed through a packed section filled with ion exchange resin.
• Another example is a method in which an ion exchange resin is added to a solution containing the compound in a processing vessel and a dispersion or suspension process is carried out, and then the ion exchange resin is separated and removed by a method such as filtration to obtain a solution that has been subjected to a purification process.
• the product to be purified may be treated multiple times with the same ion exchange resin, or the product to be purified may be treated with different ion exchange resins.
• Ion exchange resins include cation exchange resins and anion exchange resins. It is preferable to use at least a cation exchange resin because it is easy to adjust the content of metal components and make the mass ratio of the acid component content to the metal component content within the above range, and it is more preferable to use an anion exchange resin together with a cation exchange resin because the content of acid components can be adjusted.
• the liquid may be passed through a filling section filled with a mixed resin containing both resins, or may be passed through multiple filling sections filled with each resin.
• cation exchange resin known cation exchange resins can be used, among which gel-type cation exchange resins are preferred.
• Specific examples of cation exchange resins include sulfonic acid-type cation exchange resins and carboxylic acid-type cation exchange resins.
• cation exchange resin commercially available products can be used, such as Amberlite IR-124, Amberlite IR-120B, Amberlite IR-200CT, ORLITE DS-1, ORLITE DS-4 (all manufactured by Organo Corporation), Duolite C20J, Duolite C20LF, Duolite C255LFH, Duolite C-433LF (all manufactured by Sumika Chemtex Corporation), DIAION SK-110, DIAION SK1B, and DIAION SK1BH (all manufactured by Mitsubishi Chemical Corporation), Purolite S957, and Purolite S985 (all manufactured by Purolite Corporation), etc.
• Amberlite IR-124, Amberlite IR-120B, Amberlite IR-200CT, ORLITE DS-1, ORLITE DS-4 all manufactured by Organo Corporation
• anion exchange resin known anion exchange resins can be used, and among them, it is preferable to use a gel-type anion exchange resin.
• acid components present as ions in the product to be purified include inorganic acids derived from catalysts used in the production of the product to be purified, and organic acids (e.g., reaction raw materials, isomers, and by-products) generated after reactions in the production of the product to be purified.
• organic acids e.g., reaction raw materials, isomers, and by-products
• HSAB Hard and Soft Acids and Bases
• an anion exchange resin containing a hard base to a medium hard base is preferable to use in order to increase the removal efficiency when removing these acid components by interaction with the anion exchange resin.
• the anion exchange resin containing such a hard base to a moderately hard base is preferably at least one selected from the group consisting of a type I anion exchange resin of a strong base type having a trimethylammonium group, a type II anion exchange resin of a slightly weakly strong base type having a dimethylethanolammonium group, and a weak base type anion exchange resin such as dimethylamine and diethylenetriamine.
• organic acids are hard acids, and among inorganic acids, sulfate ions are acids of moderate hardness. Therefore, by using the above-mentioned strong base type or slightly weak strong base type anion exchange resin in combination with a moderately weak base type anion exchange resin, it becomes easy to reduce the content of the acid components to a suitable range.
• anion exchange resins commercially available products can be used, such as Amberlite IRA-400J, Amberlite IRA-410J, Amberlite IRA-900J, Amberlite IRA67, ORLITE DS-2, ORLITE DS-5, ORLITE DS-6 (manufactured by Organo Corporation), Duolite A113LF, Duolite A116, Duolite A-375LF (manufactured by Sumika Chemtex Corporation), and DIAION SA12A, DIAION SA10A, DIAION SA10AOH, DIAION SA20A, DIAION WA10 (manufactured by Mitsubishi Chemical Corporation).
• anion exchange resins containing the above-mentioned hard bases to bases of medium hardness include ORLITE DS-6 and ORLITE DS-4 (both manufactured by Organo Corporation), DIAION SA12A, DIAION SA10A, DIAION SA10AOH, DIAION SA20A, and DIAION WA10 (all manufactured by Mitsubishi Chemical Corporation), Purolite A400, Purolite A500, and Purolite A850 (all manufactured by Purolite Corporation), etc.
• Ion adsorption by chelating groups can be performed, for example, by using a chelating resin having a chelating group.
• the chelating resin does not release substitute ions when capturing ions, and does not use a chemically highly active functional group such as a strong acid or strong base, thereby suppressing side reactions such as hydrolysis and condensation reactions with the organic solvent to be purified. Therefore, purification can be performed more efficiently.
• the chelating resin examples include resins having chelating groups or chelating ability, such as an amidoxime group, a thiourea group, a thiouronium group, iminodiacetic acid, amidophosphoric acid, phosphonic acid, aminophosphoric acid, aminocarboxylic acid, N-methylglucamine, an alkylamino group, a pyridine ring, a cyclic cyanine, a phthalocyanine ring, and a cyclic ether.
• chelating groups or chelating ability such as an amidoxime group, a thiourea group, a thiouronium group, iminodiacetic acid, amidophosphoric acid, phosphonic acid, aminophosphoric acid, aminocarboxylic acid, N-methylglucamine, an alkylamino group, a pyridine ring, a cyclic cyanine, a phthalocyanine ring, and a cyclic ether.
• chelating resin commercially available products can be used, such as Duolite ES371N, Duolite C467, Duolite C747UPS, Sumichilate MC760, Sumichilate MC230, Sumichilate MC300, Sumichilate MC850, Sumichilate MC640, and Sumichilate MC900 (all manufactured by Sumika Chemtex Co., Ltd.), Purolite S106, Purolite S910, Purolite S914, Purolite S920, Purolite S930, Purolite S950, Purolite S957, and Purolite S985 (all manufactured by Purolite Co., Ltd.).
• Duolite ES371N Duolite C467
• Duolite C747UPS Duolite C747UPS
• Sumichilate MC760 Sumichilate MC230
• Sumichilate MC300 Sumichilate MC300
• Sumichilate MC850 Sumichilate MC640
• the method for carrying out ion adsorption is not particularly limited, and any known method can be used.
• a typical example is a method in which the material to be purified is passed through a packed section filled with a chelating resin.
• the material to be purified may be passed through the same chelating resin multiple times, or the material to be purified may be passed through different chelating resins.
• the filling section usually includes a container and the above-mentioned ion exchange resin filled in the container.
• the container include a column, a cartridge, and a packed tower, but other containers than those exemplified above may be used as long as the product to be purified can pass through the container after it is filled with the ion exchange resin.
• distillation process Other purification methods include distilling the compound itself.
• the distillation method is not particularly limited, but any known method such as atmospheric distillation, reduced pressure distillation, molecular distillation, steam distillation, etc. can be used.
• [Preferred manufacturing method] (Compounds where RG is benzene)
• the compound of formula (Bz) is preferably produced by using the compound of formula (MB) as a raw material.
• the substituents and r1, r2, etc. in the compound are defined as above.
• R 1 , R, and OH are bonded to any position where they can be bonded.
• r1 and r2 in formula (MB) are selected so that the sum of r1 to r4 is equal to or less than the valence of benzene when formula (Bz) is obtained.
• An example of the compound of formula (MB) is hydroxybenzaldehyde.
• the compound of formula (Bz) can be produced by various methods, but from the viewpoint of availability of raw materials and yield, it is preferably produced by a method including the following steps: providing a compound of formula (MB); an iodination step of introducing an iodine atom into the compound; a protecting group introduction step of introducing a protecting group into the compound; and a reducing step of reducing the compound.
• Solvents that can be used in the iodination step include a wide variety of solvents, including polar aprotic solvents and protic polar solvents.
• a single protic polar solvent or a single polar aprotic solvent can be used.
• a mixture of polar aprotic solvents, a mixture of protic polar solvents, a mixture of polar aprotic solvents and protic polar solvents, and a mixture of aprotic or protic solvents and nonpolar solvents can be used, with polar protic solvents or mixtures thereof being preferred, and a mixture of polar protic solvents and water being preferred in terms of suppressing side reactions.
• a solvent is effective but not essential.
• Suitable polar aprotic solvents include, but are not limited to, ether-based solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, triglyme, etc., ester-based solvents such as ethyl acetate, ⁇ -butyrolactone, etc., nitrile-based solvents such as acetonitrile, hydrocarbon-based solvents such as toluene, hexane, etc., amide-based solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, hexamethylphosphite triamide, etc., ketone-based solvents such as acetone, ethyl methyl ketone, etc., chlorine-based solvents such as dichloromethane, chloroform, etc., dimethyl sulfoxide, etc.
• Suitable protic polar solvents include, but are not limited to, water, alcohol-based solvents such as methanol, ethanol, propanol, butanol, di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol.
• the amount of the solvent used can be appropriately set depending on the substrate, catalyst, reaction conditions, etc. used, and is not particularly limited. Generally, however, an amount of 0 to 10,000 parts by mass per 100 parts by mass of the reaction raw materials is suitable, and from the viewpoint of yield, an amount of 100 to 2,000 parts by mass is preferable.
• the raw material compounds, catalyst and solvent are added to the reactor to form a reaction mixture.
• Any suitable reactor may be used.
• the reaction may be carried out by appropriately selecting a known method such as batch, semi-batch or continuous.
• the reaction temperature is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the formed product, the choice of catalyst and the desired yield. In general, a reaction temperature of 0°C to 200°C is suitable, and from the viewpoint of yield, a reaction temperature of 0°C to 100°C is preferred, a reaction temperature of 0°C to 70°C is more preferred, and a reaction temperature of 0°C to 50°C is even more preferred. In the reaction in this embodiment, the preferred reaction temperature range is 0°C to 100°C.
• the ratio of the iodinating agent to the substrate is preferably 0.5 molar times or more, more preferably 1.0 molar times or more, and even more preferably 1.5 molar times or more.
• the reaction pressure is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the formed product, the choice of catalyst and the desired yield. The pressure can be adjusted using an inert gas such as nitrogen, or using an air pump or the like. For reactions at high pressure, conventional pressure reactors are used, including, but not limited to, shaker vessels, rocker vessels, and stirred autoclaves. In the reaction of this embodiment, the preferred reaction pressure is reduced to normal pressure, with reduced pressure being preferred.
• the reaction time is not particularly limited.
• the preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst, and the desired yield. However, most reactions are carried out in less than 6 hours, with reaction times of 15 minutes to 600 minutes being typical. In the reaction of this embodiment, the reaction time range is 15 minutes to 600 minutes, preferably 15 minutes to 600 minutes, and more preferably 15 minutes to 360 minutes. Isolation and purification can be carried out after completion of the reaction using suitable methods known in the art. For example, the reaction mixture is poured onto ice water and extracted into a solvent such as ethyl acetate or diethyl ether. The product is then recovered by removing the solvent using evaporation at reduced pressure.
• a solvent such as ethyl acetate or diethyl ether.
• the desired high-purity compounds can be isolated and purified by separation and purification methods well known in the art, such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., or a combination of these methods.
• the iodination agent is not particularly limited, and examples thereof include iodine chloride, iodine, N-iodosuccinimide, iodic acid, and hydrogen iodide (including hydroiodic acid and aqueous hydrogen iodide solution). It is preferable to use iodine and iodic acid.
• the ratio of the iodination agent to the substrate is preferably 1.2 molar times or more, more preferably 1.5 molar times or more, and even more preferably 2.0 molar times or more.
• RG is a group containing at least one cyclic structure, I is an iodine atom, R 1 is a monovalent functional group having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, which may be the same or different; n is an integer from 1 to 5; m is an integer from 1 to 5.
• I, R, A and Z are defined the same as in formula (Bz).
• R 1' is a monovalent functional group, which may be the same or different, having 0 to 30 carbon atoms and not containing a polymerizable unsaturated bond, excluding a hydroxyl group; r1', r2', and r4' are integers from 0 to 5, and the sum of r1', r2', and r4' is equal to or less than the valence of benzene.
• R 1' is a functional group having 0 to 30 carbon atoms, which may be the same or different, excluding a monovalent hydroxyl group that does not contain a polymerizable unsaturated bond, and is preferably not an alkyl group.
• R 1' is preferably, for example, an alkoxy group having 1 to 30 carbon atoms, a carboxyl group having 1 to 30 carbon atoms, a carboxylate group having 2 to 10 carbon atoms, an alkoxyalkyl group having 2 to 30 carbon atoms, a hydroxyalkyl group having 2 to 30 carbon atoms, an aldehyde group, a halogen atom other than an iodine atom, a nitro group, an amino group, a cyano group, or a thiol group.
• R 1' is preferably a carboxyl group, an ester group, or a hydroxyalkyl group from the viewpoint of sensitizing effect, etc.
• r1', r2', and r4' are preferably integers of 0 to 5, more preferably integers of 0 to 3, and particularly preferably integers of 0 to 2.
• r4' is preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and particularly preferably an integer of 0 to 3, provided that the sum of r1', r2', and r4' is equal to or less than the valence of benzene.
• I, R, Z and R1 ' are defined the same as in formula (Bz4).
• r1', r2', and r4' are integers from 0 to 5, and the sum of r1', r2', and r4' is equal to or less than the valence of benzene.
• I is defined as in formula (Bz4), r4' is an integer from 0 to 4, and r5' is an integer from 0 to 4.
• a wide variety of solvents including polar aprotic solvents and protic polar solvents, can be used in this step.
• a single protic polar solvent or a single polar aprotic solvent can be used.
• a mixture of polar aprotic solvents, a mixture of protic polar solvents, a mixture of polar aprotic solvents and protic polar solvents, and a mixture of aprotic or protic solvents and nonpolar solvents can be used, with polar aprotic solvents or mixtures thereof being preferred.
• the solvent is an effective but not essential component.
• Suitable polar aprotic solvents include, but are not limited to, ether-based solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, triglyme, etc., ester-based solvents such as ethyl acetate, ⁇ -butyrolactone, etc., nitrile-based solvents such as acetonitrile, hydrocarbon-based solvents such as toluene, hexane, etc., amide-based solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, hexamethylphosphite triamide, etc., ketone-based solvents such as acetone, ethyl methyl ketone, etc., chlorine-based solvents such as dichloromethane, chloroform, etc., dimethyl sulfoxide, etc.
• Suitable protic polar solvents include, but are not limited to, water, alcohol-based solvents such as methanol, ethanol, propanol, butanol, di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol.
• the amount of the solvent used can be appropriately set depending on the substrate, catalyst, reaction conditions, etc. used, and is not particularly limited. In general, 0 to 10,000 parts by mass is suitable for 100 parts by mass of the reaction raw material, and from the viewpoint of yield, 100 to 2,000 parts by mass is preferable.
• the protective introduction reagent As the protective introduction reagent, a wide variety of protective introduction reagents that function under the reaction conditions of this embodiment are used. Examples of suitable protective introduction reagents include, but are not limited to, active carboxylic acid derivative compounds such as acid halides, acid anhydrides, dicarbonates, alkyl halides, vinyl alkyl ethers, dihydropyrans, and halocarboxylic acid alkyl esters.
• the ratio of the protective group introduction agent to the substrate is not particularly limited, but is preferably 0.5 molar times or more, more preferably 1.0 molar times or more, and even more preferably 1.5 molar times or more.
• an acid catalyst or a base catalyst is preferable.
• suitable acid catalysts include, but are not limited to, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid, organic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, citric acid, fumaric acid, maleic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, dichloroacetic acid, trichloroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid, Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluor
• acid catalysts may be used alone or in combination of two or more.
• organic acids and solid acids are preferred, and from the viewpoint of production, such as ease of availability and ease of handling, it is preferred to use hydrochloric acid or sulfuric acid.
• suitable base catalysts include, but are not limited to, amine-containing catalysts such as pyridine, diisopropylethylamine, and ethylenediamine, and non-amine base catalysts such as inorganic bases, such as metal salts and particularly potassium or acetate salts, and suitable catalysts include, but are not limited to, potassium acetate, potassium carbonate, potassium hydroxide, sodium acetate, sodium carbonate, sodium hydroxide, and magnesium oxide.
• All non-amine base catalysts of the present embodiment are commercially available, for example, from EM Science (Gibbstown) or Aldrich (Milwaukee).
• the amount of catalyst used can be appropriately set depending on the substrate, catalyst, and reaction conditions used, and is not particularly limited, but generally, 1 to 5,000 parts by mass is suitable for 100 parts by mass of reaction raw materials, and from the viewpoint of yield, 50 to 3,000 parts by mass is preferable.
• inorganic bases include, but are not limited to, sodium carbonate, potassium carbonate, sodium hydroxide, potassium hydroxide, sodium metasilicate, potassium metasilicate, etc., and among these, sodium carbonate and potassium carbonate are preferably used.
• amide solvents include, but are not limited to, N-methyl-2-pyrrolidone (NMP), N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMAc), etc., and among these, DMF is preferred. These may be used alone or in combination of two or more.
• NMP N-methyl-2-pyrrolidone
• DMF N,N-dimethylformamide
• DMAc N,N-dimethylacetamide
• HCl produced as a by-product in the protecting group introduction step contributes to the decomposition reaction of the product, but by using an inorganic base, the inorganic base reacts with HCl, thereby suppressing the decomposition of the product.
• the component produced by the reaction of the inorganic base with HCl is insoluble in the amide solvent and goes outside the reaction system, thereby suppressing decomposition of the product.
• the compound having a hydroxy group to which a protecting group is introduced include compounds of the formulae (Bz) and (Bz4) in which R 1 is a hydroxy group.
• a protecting group may be introduced into R 1 .
• the protective compound, catalyst and solvent are added to the reactor to form a reaction mixture.
• Any suitable reactor may be used.
• the reaction may be carried out by any known method, such as batch, semi-batch or continuous.
• the reaction temperature is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield. In general, a temperature of 0°C to 200°C is suitable, and from the viewpoint of yield, a temperature of 10°C to 190°C is preferred, a temperature of 25°C to 150°C is more preferred, and a temperature of 50°C to 100°C is even more preferred. In the reaction in this embodiment, the preferred temperature range is 0°C to 100°C.
• the reaction pressure is not particularly limited.
• the preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst and the desired yield.
• the pressure can be adjusted using an inert gas such as nitrogen, or using an air pump or the like.
• conventional pressure reactors are used, including, but not limited to, shaker vessels, rocker vessels, and stirred autoclaves.
• the preferred reaction pressure is reduced pressure to normal pressure, with reduced pressure being preferred.
• the reaction time is not particularly limited.
• the preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of catalyst, and the desired yield. However, most reactions are carried out in less than 6 hours, with reaction times of 15 minutes to 600 minutes being typical. In the reaction of this embodiment, the preferred reaction time range is 15 minutes to 600 minutes.
• Isolation and purification can be carried out after the reaction is completed using any suitable method known in the art.
• the reaction mixture is poured onto ice water and extracted into a solvent such as ethyl acetate or diethyl ether.
• the product is then recovered by removing the solvent using evaporation at reduced pressure.
• the desired high purity monomer can be isolated and purified by separation and purification methods such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., which are well known in the art, or a combination thereof.
• a wide variety of solvents including polar aprotic solvents and protic polar solvents are used as solvents that can be used in the reduction step.
• a single protic polar solvent or a single polar aprotic solvent can be used.
• a mixture of polar aprotic solvents, a mixture of protic polar solvents, a mixture of polar aprotic solvents and protic polar solvents, and a mixture of aprotic or protic solvents and nonpolar solvents can be used, with polar aprotic solvents or mixtures thereof being preferred, and a mixture of polar aprotic solvents and polar protic solvents being preferred from the viewpoint of suppressing side reactions, and as polar protic solvents, water, and alcohol-based solvents such as methanol, ethanol, propanol, and butanol are more preferred.
• Suitable polar aprotic solvents include, but are not limited to, ether-based solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, triglyme, etc., ester-based solvents such as ethyl acetate, ⁇ -butyrolactone, etc., nitrile-based solvents such as acetonitrile, hydrocarbon-based solvents such as toluene, hexane, etc., amide-based solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, hexamethylphosphite triamide, etc., ketone-based solvents such as acetone, ethyl methyl ketone, etc., chlorine-based solvents such as dichloromethane, chloroform, etc., dimethyl s
• Suitable protic polar solvents include, but are not limited to, water, alcohol-based solvents such as methanol, ethanol, propanol, butanol, di(propylene glycol) methyl ether, di(ethylene glycol) methyl ether, 2-butoxyethanol, ethylene glycol, 2-methoxyethanol, propylene glycol methyl ether, n-hexanol, and n-butanol.
• the amount of the solvent used can be appropriately set depending on the substrate, reducing agent, reaction conditions, etc. used, and is not particularly limited. Generally, however, an amount of 0 to 10,000 parts by mass per 100 parts by mass of the reaction raw materials is suitable, and from the viewpoint of yield, an amount of 100 to 2,000 parts by mass is preferable.
• Suitable reducing agents include, but are not limited to, metal hydrides, metal hydrogen complex compounds, and the like, such as borane dimethylsulfide, diisobutylaluminum hydride, sodium borohydride, lithium borohydride, potassium borohydride, zinc borohydride, lithium tri-s-butylborohydride, potassium tri-s-butylborohydride, lithium triethylborohydride, lithium aluminum hydride, lithium tri-t-butoxyaluminum hydride, sodium bis(methoxyethoxy)aluminum hydride, and the like.
• metal hydrides such as borane dimethylsulfide, diisobutylaluminum hydride, sodium borohydride, lithium borohydride, potassium borohydride, zinc borohydride, lithium tri-s-butylborohydride, potassium tri-s-butylborohydride, lithium triethylborohydride, lithium aluminum hydride, lithium tri-t-but
• the amount of reducing agent used can be set appropriately depending on the substrate, reducing agent, and reaction conditions used, and is not particularly limited. Generally, however, 1 to 500 parts by mass per 100 parts by mass of reaction raw materials is suitable, and from the viewpoint of yield, 10 to 200 parts by mass is preferable.
• the quenching agent As the quenching agent, a wide variety of quenching agents that function under the reaction conditions of this embodiment are used.
• the quenching agent has the function of deactivating the reducing agent.
• the quenching agent is effective but not essential. Suitable quenching agents include, but are not limited to, ethanol, ammonium chloride water, water, hydrochloric acid, sulfuric acid, and the like.
• the amount of the quenching agent used can be appropriately set according to the amount of the reducing agent used, and is not particularly limited, but generally, 1 to 500 parts by mass per 100 parts by mass of the reducing agent is suitable, and from the viewpoint of yield, 50 to 200 parts by mass is preferable.
• the compound to be reduced, the reducing agent and the solvent are added to a reactor to form a reaction mixture.
• Any suitable reactor may be used.
• the reaction may be carried out in a batch, semi-batch or continuous manner, as well as in other known processes.
• the reaction temperature is not particularly limited. The preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of the reducing agent and the desired yield. In general, temperatures between 0°C and 200°C are suitable, and from the viewpoint of yield, temperatures between 0°C and 100°C are preferred, temperatures between 0°C and 70°C are more preferred, and temperatures between 0°C and 50°C are even more preferred.
• the preferred temperature range is between 0°C and 100°C.
• the reaction pressure is not particularly limited.
• the preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of the reducing agent and the desired yield.
• the pressure can be adjusted using an inert gas such as nitrogen, or using an air pump or the like.
• conventional pressure reactors are used, including but not limited to shaker vessels, rocker vessels and stirred autoclaves.
• the preferred reaction pressure is reduced pressure to normal pressure, with reduced pressure being preferred.
• the preferred range depends on the concentration of the substrate, the stability of the product formed, the choice of reducing agent and the desired yield. However, most reactions are carried out in less than 6 hours, with reaction times of 15 to 600 minutes being typical.
• the reaction time range is preferably 15 to 600 minutes, more preferably 15 to 360 minutes.
• Isolation and purification can be carried out after the reaction is completed using any suitable method known in the art.
• the reaction mixture is poured onto ice water and extracted into a solvent such as ethyl acetate or diethyl ether.
• the product is then recovered by removing the solvent using evaporation under reduced pressure.
• the desired high purity compound can be isolated and purified by separation and purification methods such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, etc., which are well known in the art, or a combination thereof.
• the reduction step preferably includes a step of esterifying the carboxylic acid and a step of reducing the obtained ester group to convert it into a hydroxymethyl group.
• the ester group refers to a structure consisting of a carbonyl group derived from a carboxylic acid and an alkoxy group derived from an alcohol.
• the carboxylic acid a carboxylic acid halide or a carboxylic acid anhydride can also be used.
• R 1 when R 1 is a carboxylic acid, a compound represented by the following formula (Bz5) is preferable.
• a carboxylic acid connected to an electrically attractive group is preferable, and for example, a compound represented by the following formula (Bz5) that is an aromatic carboxylic acid having an iodine atom as a substituent can be mentioned.
• I, Z, R 1 , A, R, and r1 to r4 are defined the same as in formula (DM1a).
• the esterification agent used in the esterification step is not particularly limited, but examples thereof include acid catalysts, base catalysts, carbodiimide-based condensing agents, phosgene derivative-based condensing agents, etc., and it is preferable to use an acid catalyst, base catalyst, or carbodiimide-based condensing agent.
• the acid catalyst and base catalyst are not particularly limited, and the same ones as those described above can be used.
• the solvent is not particularly limited, but examples thereof include THF, DMSO, chloroform, toluene, etc., and it is preferable to use THF.
• the reducing agent used in the process of reducing the ester group to convert it to a hydroxy group is not particularly limited, but includes boron-based reducing agents and lithium-based reducing agents, etc. It is preferable to use a boron-based reducing agent such as sodium borohydride or borane, and it is more preferable to use a reducing agent in combination with calcium chloride or lithium chloride.
• the solvent is not particularly limited, but includes THF, DMSO, chloroform, toluene, etc. It is preferable to use toluene, and it is more preferable to use it in combination with methanol.
• a process of reducing the ester group to convert it to a hydroxy group may be performed without purification.
• the compound of formula (N) is preferably prepared by using a compound represented by formula (MN) as a raw material.
• the substituents, s3, s4, etc. are defined as above.
• s3 and s4 in formula (MN) are selected so that the sum of s1 to s4 is equal to or less than the valence of naphthalene when formula (N) is obtained.
• R 1 is not limited, but examples thereof include a hydroxyl group, an amino group, a nitro group, a halogen atom other than an iodine atom, an aldehyde group, etc.
• Specific examples of the compound of formula (MN) are not limited, but examples thereof include (di)hydroxynaphthaldehyde, aminosinaphthaldehyde, nitronaphthaldehyde, and chloronaphthaldehyde.
• the compound of formula (N) can be produced by various methods, but from the viewpoint of availability of raw materials and yield, it is preferably produced by a method including the following steps: From the viewpoint of availability of raw materials and yield, it is preferable to produce it by a method including the following steps. providing a compound of formula (MN); an iodination step of introducing an iodine atom into the compound; a protecting group introduction step of introducing a protecting group into the compound; and a reducing step of reducing the compound.
• the compound of formula (Ad) can be produced by various methods. From the viewpoints of availability of raw materials and yield, it is preferable to produce it by a method including the following steps: a preparation step of preparing a compound of formula (MA), and an iodination step of introducing an iodine atom.
• the method for producing the compound represented by formula (1) in order to improve productivity, 1) preparing a compound represented by formula (Ad-A-3-0); 2) preparing a compound represented by formula (Ad-A-3-1); and 3) preparing a compound represented by formula (Ad-A-3-2); It is preferable that the method includes any one or more steps selected from the following:
• the method includes a step of preparing a compound represented by formula (Ad-A-3-0), 1) preparing a compound represented by formula (Ad-A-3-0); 2) an oxidation step of oxidizing a compound represented by formula (Ad-A-3-0); 3) esterifying the carboxylic acid of the obtained compound; 4) an iodination step of iodizing the solution; 5) a step of hydrolyzing the ester group of the obtained compound to convert it into a carboxyl group.
• a step of preparing a compound represented by formula (Ad-A-3-0) 1) preparing a compound represented by formula (Ad-A-3-0); 2) an oxidation step of oxidizing a compound represented by formula (Ad-A-3-0); 3) esterifying the carboxylic acid of the obtained compound; 4) an iodination step of iodizing the solution; 5) a step of hydrolyzing the ester group of the obtained compound to convert it into a carboxyl group.
• the oxidation process for oxidizing the compound represented by formula (Ad-A-3-0) is not particularly limited, but examples thereof include a method using an oxidizing agent, a method of hydrolyzing a bromide, and a method of oxygen oxidation using an imide compound.
• the oxidizing agent include, but are not particularly limited to, air, oxygen, ozone, nitric acid, halogens (chlorine, bromine, iodine), potassium nitrate, hypochlorous acid, permanganate, cerium ammonium nitrate, chromic acid, peroxide, Tollens' reagent, and ruthenium compounds, and it is preferable to use a ruthenium compound.
• ruthenium compound examples include, but are not particularly limited to, ruthenium metal, ruthenium dioxide, ruthenium tetroxide, ruthenium hydroxide, ruthenium chloride, ruthenium bromide, ruthenium iodide, ruthenium sulfate, or hydrates thereof. These can be used alone or in mixtures.
• ruthenium compounds ruthenium chloride, ruthenium dioxide, or hydrates thereof are particularly preferred from the viewpoint of easily reacting with periodate or hypochlorite used as a co-oxidizing agent to produce highly oxidized ruthenium having a highly active catalytic function.
• periodate potassium periodate, sodium periodate, and calcium periodate are preferred, and sodium periodate is more preferred.
• One or more types of oxidizing agents and co-oxidizing agents can be used.
• the process of esterifying the carboxylic acid of the obtained compound may be the same as the esterification process in formula (Bz).
• the step of hydrolyzing the ester group of the obtained compound to convert it to a carboxyl group is not particularly limited, but it is preferable to hydrolyze it to a carboxyl group using an acid catalyst or a base catalyst, and it is preferable to use a base catalyst from the viewpoint of the selectivity of hydrolysis.
• the acid catalyst is not particularly limited, but examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid; organic acids such as oxalic acid, formic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, naphthalenesulfonic acid, and naphthalenedisulfonic acid; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride; and solid acids such as silicotungstic acid, phosphotungstic acid, silicomolybdic acid, and phosphomolybdic acid.
• inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, hydrobromic acid, and hydrofluoric acid
• organic acids such as oxalic acid, formic acid, p-tol
• the base catalyst is not particularly limited, but examples thereof include organic base catalysts such as pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, imidazole, N,N-dimethylaniline, and N,N-diethylaniline, and inorganic base catalysts such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, and sodium hydrogen carbonate, with inorganic salt catalysts being preferred, and potassium hydroxide and sodium hydroxide being more preferred.
• organic base catalysts such as pyridine, quinoline, isoquinoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, trimethylamine, triethylamine, tripropylamine, tributylamine, imidazole, N,N-
• the iodination process for iodinating the compound represented by formula (Ad-A-3-0) may be the same as the iodination process described above.
• the method further comprises the step of 4) preparing a compound represented by formula (Ad-A-3): It is preferred that the compound contains
• the method includes a step of preparing a compound represented by formula (Ad-A-3), 1) preparing a compound represented by formula (Ad-A-3); 2) a reduction step of reducing the compound represented by formula (Ad-A-3).
• the reduction process for reducing the obtained compound may be the same as the reduction process described above.
• the solvents that can be used in the iodination step are those listed in the method for producing a compound in which RG is benzene.
• the raw material compound, catalyst, and solvent are added to a reactor to form a reaction mixture.
• the reaction conditions, etc. can also be the same as those described in the method for producing a compound in which RG is benzene.
• the iodination step preferably includes concentrating the reaction solution by distilling off water in a reaction to obtain an alkyl iodide using an aqueous hydrogen iodide solution and adamantane alcohol as raw materials.
• the hydrogen iodide concentration in the reaction solution is preferably 10% or more, more preferably 25% or more, even more preferably 40% or more, particularly preferably 45% or more, and most preferably 50% or more.
• the hydrogen iodide concentration in the aqueous phase containing hydrogen iodide is the above concentration.
• Adamantane alcohol may have only one hydroxyl group in the molecule, or two or more.
• the hydroxyl group to be iodized may be primary, secondary, or tertiary, but is preferably secondary or tertiary, and more preferably tertiary.
• the adamantane alcohol is preferably represented by the following formula (MA-1).
• R 1 and R" are defined the same as in formula (Ad).
• R 1 is preferably -OH, -NO 2 , or a monovalent group having 1 to 12 carbon atoms which may contain at least one functional group.
• the functional group is one or more groups selected from the group consisting of a hydroxyl group, an ether group, an ester group, a carboxyl group, a halogen atom, -NO 2 , and NLL'.
• Each of the L and L' is independently a hydrogen atom, a hydroxyl group, or a monovalent group having 1 to 12 carbon atoms which may contain at least one functional group.
• the amount of hydrogen iodide is preferably 1.01 equivalents or more relative to the hydroxyl groups to be iodized, more preferably 1.1 equivalents or more, even more preferably 1.3 equivalents or more, and particularly preferably 1.5 equivalents or more.
• a method for selectively leaving one or more hydroxyl groups may include, for example, a step of performing iodination in a multiphase system including an organic phase containing an organic solvent as a solvent and an aqueous phase containing water as a solvent.
• the organic solvent may be a hydrophobic solvent, and the hydrophobic solvent refers to a solvent that is not miscible with water in any ratio.
• the iodination of the hydroxyl groups proceeds in the aqueous phase. It is possible to obtain an alkyl iodide having one or more hydroxyl groups remaining by extracting an alkyl iodide having one or more hydroxyl groups remaining from an alcohol having two or more hydroxyl groups into the hydrophobic solvent phase. In addition, by extracting the resulting alkyl iodide into the hydrophobic solvent phase, the yield loss caused by side reactions can be suppressed, so the use of a hydrophobic solvent is also effective when iodizing all hydroxyl groups.
• the hydrophobic solvent may or may not form an azeotropic mixture with water, but a hydrophobic solvent that forms an azeotropic mixture with water is preferred.
• hydrophobic solvents that form an azeotropic mixture with water include dichloromethane, chloroform, carbon tetrachloride, nitromethane, 1,2-dichloroethane, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl isobutyl ketone, pentane, cyclohexane, hexane, benzene, toluene, o-xylene, m-xylene, p-xylene, cumene, nitrobenzene, phenol, s-butanol, cyclopentyl methyl ether, and cyclohexanone, with hexane, toluene, o-xylene, m-xylene, and
• the hydrophobic solvent is preferably used in an amount of 50 equivalents or less by mass relative to the raw material alcohol, more preferably 30 equivalents or less, and even more preferably 20 equivalents or less.
• An acid may be used in the reaction.
• acids include sulfuric acid, nitric acid, phosphoric acid, p-toluenesulfonic acid, methanesulfonic acid, benzenesulfonic acid, acetic acid, trifluoroacetic acid, citric acid, oxalic acid, malic acid, lactic acid, glycolic acid, succinic acid, chromic acid, and boric acid.
• a metal iodide in combination during the reaction.
• the combined use of LiI, NaI, KI, MgI2 , CaI2 , AlI3 , etc. is effective.
• Stirring blades of various shapes can be used, such as flat paddle blades, inclined paddle blades, turbine blades, disk turbine blades, propeller blades, three-blade swept-back blades, anchor blades, helical ribbon blades, screw blades, anchor blades, Max Blend, Full Zone, Twin Star, etc.
• the stirring speed can be any speed.
• the stirring speed may be set to a speed at which the interface fluctuates, at which some oil or water droplets are generated and dispersed, or at which a completely dispersed state is achieved.
• the reaction time for iodination can also be shortened by allowing the substrate and iodinating agent to stand and then stirring.
• the standing time is preferably 1 to 48 hours, more preferably 4 to 24 hours, and even more preferably 8 to 12 hours.
• the reaction temperature is preferably 0 to 150°C, more preferably 20 to 150°C, and even more preferably 50 to 120°C.
• the reaction temperature In order to distill off water, the reaction temperature must be the boiling point of the reaction liquid. If the boiling point fluctuates due to the use of a hydrophobic solvent, the reaction temperature can be controlled by reducing or increasing the pressure of the reaction.
• the reaction temperature can also be controlled by changing the stirring speed.
• a hydrophobic solvent forms an azeotrope with water
• the azeotropic point will be lower than the boiling point of the solvent.
• a hydrophobic solvent that forms an azeotrope with water is used and the reaction liquid is separated into two liquid-liquid phases, the two phases approach a completely dispersed state as the stirring speed increases, and the boiling point also approaches the azeotropic point, so the reaction temperature can be controlled by the stirring speed.
• the entire amount of water distilled off by simple distillation may be distilled off, or the required amount may be distilled off using a Dean-Stark apparatus or the like, but it is preferable to distill off the required amount using a Dean-Stark apparatus or the like.
• the amount of water to be distilled off is preferably determined so as to maintain the hydrogen iodide concentration at a predetermined concentration or higher.
• the above concentration is preferably at least 15% lower than the hydrogen iodide concentration charged, more preferably at least 10% lower than the hydrogen halide concentration charged, even more preferably at least 5% lower than the hydrogen iodide concentration charged, and particularly preferably at least the hydrogen iodide concentration charged.
• a fixed amount of water may be distilled off continuously, or may be distilled off all at once at predetermined time intervals. After completion of the reaction, an operation is carried out to purify and isolate the alkyl iodide.
• elemental iodine is produced by oxidation of hydrogen iodide. If elemental iodine remains, it can cause discoloration, so it is preferable to reduce it to hydrogen iodide using a reducing agent.
• reducing agent There are no particular restrictions on the type of reducing agent, but examples include sodium sulfite, sodium hydrogen sulfite, and phosphinic acid.
• a preferred method for removing elemental iodine is to add an iodide salt to the reaction solution and remove the elemental iodine by transferring it to the aqueous layer.
• Potassium iodide, etc. can be used as the iodide salt.
• the reducing agent may be added directly to the reaction solution, or may be added as an aqueous solution.
• the reducing agent may be added while hydrogen iodide remains in the reaction solution, or may be added after neutralizing the hydrogen iodide with a base.
• the base used in the neutralization step examples include sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, and sodium bicarbonate.
• the iodination process is also preferably a method using a combination of trimethylsilyl chloride, sodium iodide or potassium iodide, and adamantane alcohol as raw materials.
• the solvent is preferably a polar aprotic solvent, and is not limited thereto, but examples thereof include ether-based solvents such as diethyl ether, tetrahydrofuran, dimethoxyethane, diglyme, and triglyme, ester-based solvents such as ethyl acetate and ⁇ -butyrolactone, nitrile-based solvents such as acetonitrile, hydrocarbon-based solvents such as toluene and hexane, amide-based solvents such as N,N-dimethylformamide, 1-methyl-2-pyrrolidinone, N,N-dimethylacetamide, hexamethylphosphoramide, and hexamethylphosphite triamide, ketone-based
• Acetonitrile is the most preferable.
• the ratio of trimethylsilyl chloride to sodium iodide used is preferably 1.0 molar equivalent or more, more preferably 1.5 molar equivalent or more, and even more preferably 2.0 molar equivalent or more.
• the reaction temperature is preferably reflux.
• the concentration method, type of reducing agent, stirring speed, filter form, etc. can be the same as those in the iodination reaction using hydrogen iodide described above.
• adamantane polyol when introducing multiple iodines, it is preferable to use hydrogen iodide as the iodinating agent, and when introducing one iodine atom, it is preferable to use a combination of trimethylsilyl chloride and sodium iodide or potassium iodide as the iodinating agent.
• hydrophobic solvent When a hydrophobic solvent is used, purification is possible by washing the hydrophobic solvent phase with water.
• water For example, pure water, an aqueous sodium chloride solution, an aqueous nitric acid solution, an aqueous oxalic acid solution, an aqueous sulfuric acid solution, an aqueous hydrogen chloride solution, etc. can be suitably used for washing with water.
• a hydrophobic solvent after completion of the reaction and perform washing with water.
• the hydrophobic solvent added after completion of the reaction may be the same as the hydrophobic solvent used in the reaction, or it may be different.
• washing with water is carried out at around room temperature, but if the product precipitates when washing with water at room temperature, it is possible to wash with water while heating.
• the washing temperature is preferably below the azeotropic temperature of the hydrophobic solvent and water.
• purification is also possible by passing the liquid through an ion exchange resin, chelating resin, metal removal filter, or particulate removal filter.
• Ion exchange resins, chelating resins, metal removal filters, and particulate removal filters may be used alone during purification, or in combination with operations such as water washing.
• the compound of formula (Ad) can be isolated by distillation or crystallization.
• the distillation method is not particularly limited, but for example, methods such as batch simple distillation, equilibrium flash distillation, batch rectification, and continuous rectification can be suitably applied.
• the compound of formula (Ad) may be recovered by distillation, or may be recovered as a bottoms liquid or bottoms liquid.
• the hydrophobic solvent used in the reaction may be used as is, or a new solvent may be added.
• the solvent may be a single solvent, or two or more types of solvents may be used in combination.
• the solvent used during crystallization is preferably 20 equivalents or less, more preferably 10 equivalents or less, even more preferably 5 equivalents or less, and particularly preferably 3 equivalents or less, in terms of mass ratio relative to the compound of formula (Ad). It is also possible to adjust the ratio of the solvent to the compound of formula (Ad) by distilling off the solvent.
• Crystals may be precipitated by adding seed crystals, or by cooling the solution without adding seed crystals. After crystal precipitation, the slurry is cooled to improve yield.
• the cooling rate is preferably 30°C/h or less, more preferably 20°C/h or less, even more preferably 10°C/h or less, and particularly preferably 5°C/h or less.
• the temperature at which the slurry is subjected to solid-liquid separation after cooling is preferably -50 to 40°C, more preferably -20 to 30°C, and even more preferably -20 to 10°C.
• the method of solid-liquid separation is not particularly limited, but methods such as Nutsche filtration, centrifugation, and pressure filtration can be suitably applied.
• compound (Da2) when iodinating compound (MA), a base or an oxidizing agent can be used.
• the base or oxidizing agent has high activity, compound (Da2) can be synthesized.
• the base include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, calcium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate.
• the oxidizing agent include, but are not limited to, periodic acid, hydrogen peroxide, and certain additives (hydrochloric acid, sulfuric acid, nitric acid, p-toluenesulfonic acid, etc.).
• compound (Da2) can also be synthesized by condensing the hydroxyl groups of compound (MA) together using a strong acid or the like.
• the method for producing the compound (B) described in the present invention preferably further includes a step of treatment using an adsorbent.
• the method for producing the compound (B) may involve removing impurities using an adsorbent, or multiple types of filter filtration and adsorbents may be used in appropriate combination.
• adsorbents include known adsorbents, such as inorganic adsorbents such as alumina, activated alumina, silica gel, silica-alumina, and zeolite (synthetic zeolite, etc.), mica, and organic adsorbents such as activated carbon, molecular sieves, and ion exchange resins.
• the target component When a clean solid surface comes into contact with a target organism, the target component is adsorbed to the surface due to the interaction between the solid surface atoms and the target component, and this adsorption action can be used to adsorb and remove specific components.
• the adsorption phenomenon can be classified into two types: physical adsorption (physisorption) and chemical adsorption (chemisorption).
• physical adsorption is a phenomenon in which atoms or molecules are adsorbed onto a solid surface, where the adsorption is mainly due to van der Waals forces between gas molecules and surface atoms.
• the removal of impurities using an adsorbent is not particularly limited as long as the adsorbent is brought into contact with the compound (B) that coexists with the impurities.
• the adsorbent is added to the reaction solution (also called silica dispersion), the reaction solution is passed through a column packed with an adsorbent, the compound (B) that coexists with the impurities is dissolved in an organic solvent and an adsorbent is added, or the compound (B) that coexists with the impurities is passed through a column packed with an adsorbent. From the viewpoint of productivity, it is preferable to add an adsorbent to the reaction solution.
• alumina, activated alumina, silica gel, or silica-alumina as the adsorbent, and it is more preferable to use silica gel or silica-alumina.
• composition The compound is useful as a composition.
• the compound is particularly useful as a composition for lithography, and may be a composition for use in lithography.
• a composition containing the compound will be described using a composition for lithography as an example.
• the compound exerts a sensitizing effect on the lithography composition containing the compound upon irradiation with radiation. Therefore, one aspect of this embodiment may be a method of exerting a sensitizing effect on the lithography composition upon irradiation with radiation using the compound, and it is preferable to use two or more of the compounds. The reason for this is not limited, but it is thought that the compound promotes absorption of radiation. This effect is particularly noticeable in extreme ultraviolet (EUV) irradiation.
• EUV extreme ultraviolet
• the sensitizing effect can be in a variety of forms, and when a photosensitive layer formed using a lithography composition is used as a resist film for lithography, it can be confirmed, for example, as follows.
• a PEB process (a process of performing a heat treatment after exposure) and if necessary, a development process (a process of dissolving and removing the exposed or unexposed parts with a developer) are performed, and the film thickness of the film obtained is measured.
• the exposure dose is changed, the film thickness of the obtained film is measured, and the exposure dose at which the film thickness changes rapidly is defined as the sensitivity in the surface exposure method.
• sensitivity is confirmed on the low exposure side, it can be determined that there is a sensitizing effect.
• a pattern is formed by changing the exposure amount, and the exposure amount at which the line width becomes specified after exposure is defined as the sensitivity. 2) If the sensitivity is confirmed on the lower exposure side, it can be recognized that there is a sensitization effect.
• a lithography composition containing the compound is useful for suppressing defects in a resist pattern. In particular, in pattern evaluation with extreme ultraviolet (EUV), it can also be confirmed by a reduction in defects such as pitting and bridging.
• EUV extreme ultraviolet
• the defect is caused by fluctuations in the optical exposure amount or an exposure state where the exposure amount is low and is substantially similar to a defect, but if the resist film has a sensitization effect, the fluctuations and defects are avoided by promoting absorption, and the defects are reduced.
• the compound can be directly used as a component of the composition.
• the compound may be processed into a resin (substrate (A)) or additives (acid generator (C), crosslinking agent (G), acid diffusion inhibitor (E), other components (F), etc.) that contain the compound as a partial structure, and the resin or additives may be used as components of a lithography composition.
• composition for lithography contains a compound represented by formula (1) (hereinafter also referred to as "compound (B)"), and may contain other components such as a base material (A), a solvent (S), an acid generator (C), a crosslinking agent (G), and an acid diffusion controller (E) as necessary.
• compound (B) a compound represented by formula (1)
• B may contain other components such as a base material (A), a solvent (S), an acid generator (C), a crosslinking agent (G), and an acid diffusion controller (E) as necessary.
• the composition in this embodiment contains one or more compounds (B). Although not limited, the composition preferably contains two or more compounds (B). When two or more compounds (B) are contained, the etching defects shown in the examples described below tend to be reduced. The reason why the etching defects are reduced is not clear, but it is possible that, for example, the compatibility of the compound (B) in the composition is improved, and fine defects when the film is formed are reduced. It is preferable that RG of the compound B is a group derived from benzene, naphthalene, or adamantane, which may have a substituent. When two or more compounds B are contained, the groups derived from RG may be the same or different.
• the amount of compound (B) is not limited, but when a small amount of compound (B) is present (this compound is referred to as compound (B')), the amount of compound (B') is preferably 1 ppm or more, and more preferably 10 ppm or more, of the total amount of compounds (B) from the viewpoint of the etching defect improvement effect.
• the content of compound (B"') having a lower iodine atom content in the molecule than compound (B") is preferably 40% by mass or less, more preferably 10% by mass or less, and most preferably 5% by mass or less, of the total amount of compounds (B) from the viewpoint of improving sensitivity.
• a monomer compound having a larger number of iodine atoms is represented by H
• a monomer compound having a smaller number of iodine atoms is represented by L
• a dimer compound is represented by D.
• H/L mass ratio, same below
• the method for mixing two or more types of compound (B) is not limited, but two or more types of compound (B) may be mixed, or the compounds may be simultaneously synthesized as a mixture during the process of synthesizing compound (B).
• More preferred embodiments of compound B include the following. 1) A combination of a reference compound represented by formula (1) and a compound represented by formula (1) but having a smaller number of iodine atoms than the reference compound (preferably a compound represented by formula (BP0-1) described later). 2) A combination of a reference compound represented by formula (1) and a multimer of a compound represented by formula (1) (preferably a compound represented by formula (DM0-1) described above). 3) A combination of a reference compound represented by formula (1), the compound having a small number of iodine atoms, and the multimer. Furthermore, the compound having a small number of iodine atoms may be a compound that does not contain iodine atoms.
• the composition is expected to be highly effective in ensuring stability over time, particularly due to inorganic substances and inorganic components, by including a compound represented by formula (DM0-1), and the high trapping effect of the causative components is expected to lead to improved stability over time.
• the composition is expected to contain a compound represented by formula (BP0-1), and the mechanism caused by the difference in redox potential with the compound represented by formula (1) is expected to be effective in ensuring stability over time, leading to improved stability over time caused by natural oxidation and deterioration of coexisting substances over time.
• the compound represented by formula (DM0-1) is as described above.
• the compound represented by formula (DM0-1) is preferably a compound represented by the above formula (DM1a), (Dn1), or (Da1), or the following formula (DM1a-Dt), (DM1a-Dt2), (Dn1-Dt), (Dn1-Dt2), (Da1-Dt), (Da1-Dt2), (Ba1-tl), (Ba1-x), or (Ba1-eb).
• Z, I, R 1 , A, R, and r1 to r4 are defined the same as in formula (DM1a).
• n' is an integer of 0 to 5 and not more than n, and is preferably an integer of 0 to 3.
• n' in formula (BP0-1) is preferably an integer obtained by subtracting 1 from the value of n' in formula (DM0-1).
• m' is an integer of 1 to 5 and not more than m.
• the compound of formula (BP0-1) is a type of compound represented by formula (1).
• the compound represented by formula (BP0-1) is preferably represented by the following formula.
• R, R 1 , R", A, r1 to r4, s2 to s3, and t2 to t3 are defined as above.
• a1 and r4a are integers of 0 to 4, and a1 and r4a are numbers satisfying a1+r4a ⁇ r4.
• r4 is defined as above, but is preferably synonymous with r4 in formula (Bz).
• s1b is an integer of 0 to 6, and is an integer satisfying s1b ⁇ (s1-1).
• s1 is defined as above, but is preferably synonymous with s1 in formula (N).
• t1b is an integer of 0 to 9, and is an integer satisfying t1b ⁇ (t1-1).
• t1 is defined as above, but is preferably synonymous with t1 in formula (Ad).
• the compound represented by formula (BP0-1) is preferably represented by the following formula (BP1a-Dt), (Bn1-Dt), or (Ba1-Dt).
• BP1a-Dt formula (BP1a-Dt)
• Bn1-Dt formula (Bn1-Dt)
• Ba1-Dt formula (Ba1)
• Z, R, R 1 , A, r1, r2, r3, and r4a are defined the same as in formula (BP1a).
• R 1 , R′′, A, and s2 to s4 are defined the same as in formula (Bn1).
• R 1 , R′′, t2, and t3 are defined the same as in formula (Ba1).
• a composition using a compound represented by formula (1) in combination with a compound represented by formula (DM0-1) or formula (BP0-1) has excellent storage stability.
• the reason for this is not limited, but it is presumed that the compound represented by formula (DM0-1) or formula (BP0-1) sterically or electronically captures causative substances or causative components that deteriorate storage stability.
• the lower limit of the total amount of the compounds represented by formula (DM0-1) and formula (BP0-1) relative to the entire compound represented by formula (1) is preferably 1 ppm or more, more preferably 2 ppm or more, even more preferably 5 ppm or more, and particularly preferably 10 ppm or more.
• the upper limit of the total amount is preferably 10,000 ppm or less, more preferably 8,000 ppm or less, even more preferably 5,000 ppm or less, and particularly preferably 3,000 ppm or less.
• composition further contains a compound represented by formula (DM0-1)
• compounds represented by formulas (1) and (DM0-1) satisfy the following relationship. 0.1 ⁇ [amount (mol) of compound of formula (DM0-1)] ⁇ [amount (mol) of compound of formula (1)] ⁇ 0.000001
• composition further contains a compound represented by formula (DM0-1) and a compound represented by formula (BP0-1)
• compounds represented by formula (1), formula (DM0-1), and formula (BP0-1) satisfy the following relational formula. 0.1 ⁇ ([total amount (mol) of the compound of formula (DM0-1) and the compound of formula (BP0-1)]) ⁇ [amount (mol) of the compound of formula (1)] ⁇ 0.000001
• a compound represented by formula (DM0-1) it is preferable to use a compound represented by formula (DM0-1), and more preferable are compounds represented by formula (DM1a), (Dn1), (Da1), (DM1a-Dt), (DM1a-Dt2), (Dn1-Dt), (Dn1-Dt2), (Da1-Dt), (Da1-Dt2), (Ba1-tl), (Ba1-x), or (Ba1-eb).
• dimers are particularly preferable.
• the composition contains a compound B different from the compound represented by the formula (DM1a-Dt), (DM1a-Dt2), (Dn1-Dt), (Dn1-Dt2), (Da1-Dt), (Da1-Dt2), (Ba1-tl), (Ba1-x), (Ba1-eb), formula (BP1a-Dt), (Bn1-Dt), or (Ba1-Dt), it is preferable that the compound represented by the formula (DM1a-Dt), (DM1a-Dt2), (Dn1-Dt), (Dn1-Dt2), (Da1-Dt), (Da1-Dt2), (Ba1-tl), (Ba1-x), (Ba1-eb), formula (BP1a-Dt), (Bn1-Dt), or (Ba1-Dt), has the same mother nucleus as the compound B.
• the compound represented by formula (BP1a) is preferably a compound represented by formula (BP1b).
• I, R, R 1 , A, and Z are defined as in formula (BP1a), and a11 and a12 are integers of 0 to 2 satisfying a11+a12 ⁇ r4.
• r4 is defined as above, but is preferably the same as r4 in formula (Bz) (hereinafter the same).
• the compound represented by formula (BP1b) is preferably a compound represented by formula (BP1c1).
• BP1c1 I, R, R 1 , A, and Z are defined the same as in formula (BP1a), and a11 and a12 are integers from 0 to 1 satisfying a11+a12 ⁇ r4.
• the compound represented by formula (BP1c1) is preferably a compound represented by formula (BP1d11).
• I, R, R 1 , A, and Z are defined the same as in formula (BP1a), and a11 and a12 are integers from 0 to 1 satisfying a11+a12 ⁇ r4.
• the compound represented by formula (BP1c1) is preferably a compound represented by formula (BP1d12).
• I, R, R 1 and Z are defined the same as in formula (BP1a), and a11 and a12 are integers of 0 to 1 satisfying a11+a12 ⁇ r4.
• A′ is a group having a protecting group, and is represented by -O-R a -O-R b , -O-CO-O-R b , or -O-Ra-CO-O-R b , or -O-Ra-O-CO-R b .
• R a is a linear or branched alkyl group having 1 to 3 carbon atoms.
• R b is a monovalent linear or branched alkyl group or cyclic alkyl group having 1 to 3 carbon atoms, or a divalent cyclic alkyl group, which forms a ring together with the adjacent oxygen atom.
• a cyclic structure including R a and R a may be formed. However, there is at least one A′.
• the compound represented by formula (BP1b) is preferably a compound represented by formula (BP1c2).
• I, R, R 1 , A, and Z are defined the same as in formula (BP1a), and a11 and a12 are integers from 0 to 1 satisfying a11+a12 ⁇ r4.
• the compound represented by formula (BP1c2) is preferably a compound represented by formula (BP1d21).
• I, R, R 1 , A, and Z are defined the same as in formula (BP1a), and a11 and a12 are integers from 0 to 1 satisfying a11+a12 ⁇ r4.
• the compound represented by formula (BP1c1) is preferably a compound represented by formula (BP1d22).
• I, R, and R1 are defined the same as in formula (BP1a), a11 and a12 are integers of 0 to 1 satisfying a11+a12 ⁇ r4.
• A′ is defined the same as in formula (BP1d12).
• the compound represented by formula (BP1b) is preferably a compound represented by formula (BP1c3).
• I, R, R 1 , A, and Z are defined the same as in formula (BP1a), and a11 and a12 are integers from 0 to 1 satisfying a11+a12 ⁇ r4.
• the compound represented by formula (BP1c3) is preferably a compound represented by formula (BP1d31).
• I, R, R 1 , A, and Z are defined the same as in formula (BP1a), and a11 and a12 are integers from 0 to 1 satisfying a11+a12 ⁇ r4.
• the compound represented by formula (BP1b) is preferably a compound represented by formula (BP1c4).
• the compound represented by formula (BP1c4) is preferably a compound represented by formula (BP1d41).
• I, R, and R1 are defined the same as in formula (BP1a), a11 and a12 are integers from 0 to 1 satisfying a11+a12 ⁇ r4.
• A′ is defined the same as in formula (BP1d12).
• the compound represented by formula (Bn1) is preferably a compound represented by formula (Bn1a).
• the compound represented by formula (Bn1a) is preferably a compound represented by formula (Bn1b1).
• the compound represented by formula (Bn1b1) is preferably a compound represented by formula (Bn1c11).
• the compound represented by formula (Bn1b1) is preferably a compound represented by formula (Bn1c12).
• R 1 and R′′ are defined the same as in formula (Bn1), and A′ is defined the same as in formula (BP1d12).
• the compound represented by formula (Bn1a) is preferably a compound represented by formula (Bn1b2).
• the compound represented by formula (Bn1b2) is preferably a compound represented by formula (Bn1c21).
• R 1 and R′′ are defined the same as in formula (Bn1), and A′ is defined the same as in formula (BP1d12).
• the compound represented by formula (Bn1a) is preferably a compound represented by formula (Bn1b3).
• R 1 and R′′ are defined the same as in formula (Bn1), and A′ is defined the same as in formula (BP1d12).
• the compound represented by formula (Bn1b3) is preferably a compound represented by formula (Bn1c32) below.
• R 1 and R′′ are defined as in formula (Bn1), and A′ is defined as in formula (BP1d12).
• the compound represented by formula (Ba1) is preferably a compound represented by formula (Ba1a).
• I, R 1 , and R′′ are defined the same as in formula (Ba1).
• 1c1, 1c2, and 1c3 are integers of 0 or 1 satisfying (1c1 + 1c2 + 1c3) ⁇ t1b.
• t1b is defined as above, but preferably has the same meaning as t1b in formula (Ba1) (the same applies below).
• the compound represented by formula (Ba1a) is preferably a compound represented by formula (Ba1b).
• I, R′′, and R1 are defined the same as in formula (Ba1a).
• 1c1, 1c2, and 1c3 are integers of 0 or 1 satisfying (1c1+1c2+1c3) ⁇ t1b.
• the compound represented by formula (Ba1b) is preferably a compound represented by formula (Ba1c11) below.
• I, R'', and R 1 are defined the same as in formula (Ba1a).
• 1d1 and 1d2 are integers of 0 or 1 satisfying (1d1+1d2) ⁇ t1b.
• the compound represented by formula (Ba1b) is preferably a compound represented by formula (Ba1c12) below.
• compound B comprises a compound to which a solvent is added in the composition.
• the compound to which a solvent is added include compounds represented by the following formula (Ba1-tl), (Ba1-x), or (Ba1-eb).
• I, R 1 , R′′, R d , and t1 to t3 are defined the same as in formula (Da1).
• I, R 1 , R′′, R d , and t1 to t3 are defined the same as in formula (Da1).
• I, R 1 , R′′, R d , and t1 to t3 are defined the same as in formula (Da1).
• the substrate (A) refers to a compound other than the compound (B) and a material that can be used as a resist.
• the substrate (A) may be a resin.
• the substrate (A) refers to a substrate (e.g., a substrate for lithography or a substrate for resist) that can be used as a resist for g-line, i-line, KrF excimer laser (248 nm), ArF excimer laser (193 nm), extreme ultraviolet (EUV) lithography (13.5 nm) or electron beam (EB).
• Examples of the substrate (A) include phenol novolac resin, cresol novolac resin, hydroxystyrene resin, (meth)acrylic resin, hydroxystyrene-(meth)acrylic copolymer, cycloolefin-maleic anhydride copolymer, cycloolefin, vinyl ether-maleic anhydride copolymer, and inorganic resist materials having metal elements such as titanium, tin, hafnium, and zirconium, as well as derivatives thereof.
• phenol novolak resins cresol novolak resins, hydroxystyrene resins, (meth)acrylic resins, hydroxystyrene-(meth)acrylic copolymers, and inorganic resist materials containing metal elements such as titanium, tin, hafnium, and zirconium, as well as derivatives of these.
• the weight average molecular weight of the substrate (A) is preferably 2000 to 49900, more preferably 2000 to 29900, and even more preferably 2000 to 14900, from the viewpoints of reducing defects in the film formed using the composition and achieving a good pattern shape.
• the weight average molecular weight can be a value measured using GPC in terms of polystyrene.
• the solvent in this embodiment may be any solvent that dissolves the compound (B), and any known solvent may be used as appropriate.
• the solvent include ethylene glycol monoalkyl ether acetates, ethylene glycol monoalkyl ethers, propylene glycol monoalkyl ether acetates (e.g., propylene glycol monomethyl ether acetate), propylene glycol monoalkyl ethers, lactate esters, aliphatic carboxylate esters, other esters, aromatic hydrocarbons, ketones, amide 3:9, lactones, etc.Specific examples of these include those disclosed in Patent Document 1.
• the solvent used in this embodiment is preferably a safe solvent, more preferably at least one selected from PGMEA (propylene glycol monomethyl ether acetate), PGME (propylene glycol monomethyl ether), CHN (cyclohexanone), CPN (cyclopentanone), 2-heptanone, anisole, butyl acetate, and ethyl lactate, and even more preferably at least one selected from PGMEA, PGME, CHN, CPN, and ethyl lactate.
• PGMEA propylene glycol monomethyl ether acetate
• PGME propylene glycol monomethyl ether
• CHN cyclohexanone
• CPN cyclopentanone
• 2-heptanone 2-heptanone
• anisole butyl acetate
• ethyl lactate 2-heptanone
• the amount of solid components and the amount of solvent are not particularly limited, but it is preferable that the solid components be 1-80% by mass and the solvent be 20-99% by mass, more preferably 1-50% by mass and 50-99% by mass, even more preferably 2-40% by mass and 60-98% by mass, and particularly preferably 2-10% by mass and 90-98% by mass.
• the total mass of the solid components (the sum of the solid components including optional components such as the base material (A), compound (B), acid generator (C), crosslinking agent (G), acid diffusion control agent (E), and other components (F) (hereinafter the same)) is the amount of the solid components.
• the composition of the present embodiment preferably contains one or more types of acid generators (C).
• the acid generator (C) is a material that generates an acid directly or indirectly when irradiated with any radiation selected from visible light, ultraviolet light, excimer laser, electron beam, extreme ultraviolet light (EUV), X-rays, and ion beam.
• the acid generator (C) for example, those described in International Publication No. 2013/024778 can be used.
• Two or more types of acid generators (C) can also be used in combination.
• the amount of acid generator (C) used is preferably 0.001 to 49% by mass, more preferably 1 to 40% by mass, even more preferably 3 to 30% by mass, and particularly preferably 10 to 25% by mass, of the total mass of the solid components.
• the composition of the present embodiment preferably contains one or more crosslinking agents (G).
• the crosslinking agent (G) can crosslink at least either the substrate (A) or the compound (B).
• the crosslinking agent (G) intramolecularly crosslinks or intermolecularly crosslinks the substrate (A) in the presence of an acid generated from the acid generator (C).
• acid crosslinking agents include compounds having one or more groups (hereinafter referred to as "crosslinkable groups") capable of crosslinking the substrate (A).
• crosslinkable groups capable of crosslinking the substrate (A).
• Examples of the crosslinking agent (G) having a crosslinkable group include those described in International Publication No. WO 2013/024778. Two or more crosslinking agents (G) can also be used in combination.
• the amount of crosslinking agent (G) used is preferably 0.5 to 50 mass% of the total mass of the solid components, more preferably 0.5 to 40 mass%, even more preferably 1 to 30 mass%, and particularly preferably 2 to 20 mass%.
• the blending ratio of the crosslinking agent (G) is 0.5 mass% or more, it tends to improve the effect of suppressing the solubility of the resist film in an alkaline developer and to suppress a decrease in the remaining film rate and the occurrence of swelling and meandering of the pattern, while when it is 50 mass% or less, it tends to suppress a decrease in the heat resistance of the resist.
• the composition of the present embodiment may contain an acid diffusion controller (E).
• the acid diffusion controller (E) has the effect of controlling the diffusion of the acid generated from the acid generator by radiation exposure in the resist film, and preventing undesirable chemical reactions in unexposed regions.
• the use of the acid diffusion controller (E) tends to improve the storage stability of the composition of the present embodiment.
• the use of the acid diffusion controller (E) can improve the resolution of the film formed using the composition of the present embodiment.
• the use of the acid diffusion controller (E) can suppress the line width change of the resist pattern due to the variation between the delay time before radiation exposure and the delay time after radiation exposure, and the process stability tends to be improved.
• Examples of the acid diffusion controller (E) include radiation decomposable basic compounds as described in International Publication No. 2013/024778. Two or more types of acid diffusion controllers (E) can also be used in combination.
• the amount of the acid diffusion control agent (E) is preferably 0.001 to 49% by mass, more preferably 0.01 to 10% by mass, even more preferably 0.01 to 5% by mass, and particularly preferably 0.01 to 3% by mass, based on the total mass of the solid components.
• the amount of the acid diffusion control agent (E) is within the above range, it tends to be possible to prevent a decrease in resolution, deterioration of the pattern shape, dimensional fidelity, etc. Furthermore, even if the waiting time from electron beam irradiation to heating after radiation irradiation is long, it is possible to suppress deterioration of the shape of the upper layer of the pattern.
• the amount when the amount is 10% by mass or less, it tends to be possible to prevent a decrease in sensitivity, developability of unexposed parts, etc. Furthermore, by using such an acid diffusion control agent, the storage stability of the resist composition is improved, and the resolution is improved, and changes in the line width of the resist pattern due to fluctuations in the waiting time before radiation irradiation and the waiting time after radiation irradiation can be suppressed, and process stability tends to be improved.
• the composition of the present embodiment may contain one or more of the following additives as the other component (F).
• the dissolution promoter is preferably a low molecular weight one, and examples thereof include low molecular weight phenolic compounds. Examples of low molecular weight phenolic compounds include bisphenols and tris(hydroxyphenyl)methane. Two or more dissolution promoters can be used in combination.
• the amount of the dissolution promoter is adjusted appropriately depending on the type of solid component used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.
• the dissolution controller controls the solubility and appropriately reduces the dissolution rate during development.
• a dissolution controller is preferably one that does not undergo chemical changes during steps such as baking, radiation exposure, and development of the resist film.
• the dissolution control agent is not particularly limited, but examples thereof include aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene; ketones such as acetophenone, benzophenone, and phenyl naphthyl ketone; and sulfones such as methyl phenyl sulfone, diphenyl sulfone, and dinaphthyl sulfone. Two or more dissolution control agents can be used in combination.
• aromatic hydrocarbons such as phenanthrene, anthracene, and acenaphthene
• ketones such as acetophenone, benzophenone, and phenyl naphthyl ketone
• sulfones such as methyl phenyl sulfone, diphenyl sulfone, and dinaphthyl sulfone.
• Two or more dissolution control agents can be used in combination.
• the amount of the dissolution control agent is adjusted appropriately depending on the type of compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.
• the sensitizer absorbs the energy of the irradiated radiation and transfers the energy to the acid generator (C), thereby increasing the amount of acid generated and improving the apparent sensitivity of the resist.
• Examples of such sensitizers include benzophenones, biacetyls, pyrenes, phenothiazines, and fluorenes. Two or more sensitizers can be used in combination.
• the amount of the sensitizer is appropriately adjusted depending on the type of the compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.
• the surfactant improves the coatability, striations, resist developability, etc. of the composition of this embodiment.
• the surfactant may be an anionic surfactant, a cationic surfactant, a nonionic surfactant, or an amphoteric surfactant.
• a preferred surfactant is a nonionic surfactant.
• the nonionic surfactant has good affinity with the solvent used in the production of the composition of this embodiment, and can further enhance the effect of the composition of this embodiment.
• nonionic surfactants include, but are not limited to, polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, and higher fatty acid diesters of polyethylene glycol.
• the amount of surfactant is appropriately adjusted depending on the type of the solid component used, and is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass of the total mass of the solid components.
• Organic carboxylic acids, or phosphorus oxoacids or derivatives of said oxoacids have the effect of preventing deterioration in sensitivity, improving the resist pattern shape, or improving the laying stability, etc.
• organic carboxylic acids include malonic acid as described in Patent Document 1.
• phosphorus oxoacids or derivatives thereof include phosphonic acid or derivatives such as esters thereof as described in Patent Document 1, and among these, phosphonic acid is particularly preferred.
• the above acids or derivatives can be used alone or in combination of two or more.
• the amount of the acid or derivative is adjusted appropriately depending on the type of compound used, but is preferably 0 to 49% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 1% by mass, and particularly preferably 0% by mass, of the total mass of the solid components.
• the composition of the present embodiment may contain additives other than the above-mentioned components, as necessary.
• additives include dyes, pigments, and adhesive aids.
• blending a dye or pigment is preferable because it can visualize the latent image of the exposed area and reduce the effect of halation during exposure.
• blending an adhesive aid is preferable because it can improve adhesion to the substrate.
• other additives include antihalation agents, storage stabilizers, defoamers, shape improvers, and the like, specifically 4-hydroxy-4'-methylchalcone.
• the amount of compound B is preferably 10 ppm to 10 mass% of the total mass of the solid components of the composition.
• the total mass of the solid components is the sum of the solid components including the base material (A), compound (B), acid generator (C), crosslinking agent (G), acid diffusion control agent (E), and other components (F) that are optionally used.
• the mass ratio of base material (A) to compound (B) is preferably 3:97 to 99.5:0.5, and more preferably 10:90 to 99:1. When the mass ratio is within this range, there is a tendency for high sensitivity and suppression of exposure variation in the depth direction.
• the mass ratio is more preferably 30:70 to 98:2, and even more preferably 50:50 to 97:3.
• the total amount of the base material (A) and the compound (B) is preferably 50 to 99.4% by mass of the total mass of the solid components, more preferably 55 to 95% by mass, even more preferably 60 to 95% by mass, and particularly preferably 70 to 95% by mass.
• the total amount of the base material (A) and the compound (B) is within the above range, the resolution tends to be further improved and the line edge roughness (LER) tends to be further reduced.
• the (A)/(B)/(C)/(G)/(E)/(F) mass ratio (mass%) is, relative to the total mass of the solid content of the composition of this embodiment, as follows: Preferably, 1.5 to 99.0/0.2 to 96.4/0.001 to 49/0 to 49/0.001 to 49/0 to 49, More preferably, it is 5 to 98.5/0.5 to 89/1 to 40/0 to 40/0.01 to 10/0 to 5, More preferably, it is 15 to 97.5/1 to 69/3 to 30/0 to 30/0.01 to 5/0 to 1. Particularly preferred are 25-96.5/1.5-50/3-30/0-30/0.01-3/0.
• the blending ratio of each component is selected from each range so that the total sum is 100% by mass. This blending ratio tends to provide excellent performance in terms of sensitivity, resolution, developability, etc.
• Solid content refers to the components excluding the solvent
• total mass of solid content refers to the sum of the components constituting the composition excluding the solvent being 100% by mass.
• composition of this embodiment is usually prepared at the time of use by dissolving each component in a solvent to form a homogeneous solution, and then filtering the solution, if necessary, using a filter with a pore size of about 0.2 ⁇ m, for example.
• the composition of the present embodiment can form an amorphous film by spin coating.
• the composition of the present embodiment can be applied to general semiconductor manufacturing processes.
• the composition of the present embodiment can form either a positive resist pattern or a negative resist pattern depending on the type of developer used.
• a lithography composition containing compound (B) exhibits an excellent sensitization effect in EUV exposure. Therefore, the present invention also provides a method for increasing the sensitivity of a lithography composition in EUV exposure. As described above, it is preferable to use two or more types of compound (B) in the sensitization method.
• the residual amount of metal impurities in the composition is preferably less than 1 ppm relative to the composition, more preferably less than 100 ppb, even more preferably less than 50 ppb, even more preferably less than 10 ppb, and most preferably less than 1 ppb.
• metal species classified as transition metals such as Fe, Ni, Sn, Zn, Cu, Sb, W, and Al
• the residual amount of said metal is 1 ppm or more, there is a concern that the interaction with other compounds may cause denaturation or deterioration of the material over time.
• the residual amount of alkali metals or alkalinity metals such as Na, K, Ca, and Mg, is 1 ppm or more, the amount of residual metals cannot be sufficiently reduced when the compound is used to produce resin for semiconductor processes, and there is a concern that this may cause defects due to residual metals and performance deterioration in the semiconductor manufacturing process, resulting in a decrease in yield.
• the molecular weight of the compound was measured by liquid chromatography-mass spectrometry (LC-MS) using an Acquity UPLC/MALDI-Synapt HDMS manufactured by Waters.
• LC-MS liquid chromatography-mass spectrometry
• Example 1 Compound having benzene as a parent nucleus The compound was produced according to the following scheme: The reaction was carried out under a nitrogen stream.
• Example 1a Compound 2 having a benzene core 60 ml of acetone was added to 16 g (65 mmol) of 5-iodovanillin and cooled with ice. 8.2 g (63 mmol) of diisopropylethylamine was added under nitrogen, and 6.4 ml (0.84 mol) of chloromethyl ethyl ether was added dropwise at 12°C or less. The mixture was stirred at 3°C for 15 minutes, and 100 ml of water was slowly added. The precipitate was collected by filtration and washed with water. The obtained solid was suspended and stirred in 70 ml of methanol, and filtered. The solid was dried at room temperature and used in the next step.
• Example 1b Compound 3 having a benzene core Compound 3 was obtained in the same manner as in Example 1, except that 9.38 g of ethyl vinyl ether was used instead of 12.3 g of chloromethyl ethyl ether.
• 100 ml of methylene chloride was added to 22 g (60 mmol) of 4-hydroxy-3,5-diiodobenzaldehyde and cooled on ice.
• 43.2 g (600 mmol) of ethyl vinyl ether was added under a nitrogen atmosphere, and then 1.5 g (6 mmol) of pyridinium paratoluenesulfonate was added at 10°C or less.
• Example 1c Compound 4 having a benzene core Compound 4 was obtained in the same manner as in Example 1b, except that 50.5 g of 3,4-dihydro-2H-pyran was used instead of 43.2 g of ethyl vinyl ether. The formation was confirmed by NMR and LC-MS. The molecular weight was 460.
• Example 1d Compound 5 having a benzene core Compound 5 was obtained in the same manner as in Example 1, except that 14.2 g of di-tert-butyl dicarbonate was used instead of 12.3 g of chloromethyl ethyl ether. The production was confirmed by NMR and LC-MS. The molecular weight was 474.
• Example 1e Compound 6 having a benzene core 3,5-diiodo-4-hydroxybenzyl alcohol was obtained in the same manner as in Example 1. 3,5-diiodo-4-hydroxybenzyl alcohol and THF were added and stirred to dissolve, and then phosgene (2 equivalents relative to the raw material, 20% toluene solution, manufactured by Merck) was added dropwise under ice cooling in a nitrogen atmosphere, and the mixture was further stirred for 2 hours under ice cooling. The mixture was further stirred at 25°C for 12 hours. After that, nitrogen bubbling was performed for 2 hours, and then a carbonate ester (1e0) was obtained by concentrating under reduced pressure.
• the obtained carbonate ester (1e0) was placed in chloroform, and dissolved by stirring under ice cooling. Further, 1-methylcyclopentanol (1.2 equivalents relative to the (1e0)) was added dropwise under ice cooling, and the mixture was further stirred. Further, pyridine (1.2 equivalents relative to the (1e0)) was added dropwise under ice cooling, and the mixture was further stirred. After stirring for 1 hour, the mixture was stirred at 25°C for 12 hours. Then, ion-exchanged water was added, and the organic phase was recovered. The obtained organic phase was washed with 5% sodium bicarbonate water, then washed five times with ion-exchanged water, and concentrated under reduced pressure to obtain Compound 6. The production was confirmed by NMR and LC-MS. The molecular weight was 502.
• Example 1f Compound 7 with benzene as the parent structure Compound 7 was obtained in the same manner as in Example 1, except that 10.5 g of chloromethyl methyl ether was used instead of 12.3 g of chloromethyl ethyl ether. The production was confirmed by NMR and LC-MS. The molecular weight was 420.
• Example 1g Compound 8 having a benzene core
• the compound was prepared according to the following scheme: The reaction was carried out under a nitrogen stream.
• Example 1i Compound 10 (1) having a benzene core
• the compound was prepared according to the following scheme: The reaction was carried out under a nitrogen stream.
• Example 1j Compound 10 (2) having a benzene core The procedure of Example 1i was repeated except that sodium borohydride was used instead of lithium aluminum hydride, to obtain 0.1 g of compound 10 (yield 1%).
• the reaction solution was concentrated under reduced pressure, and 25 mL of water and sodium carbonate were added to make the mixture alkaline. Then, 50 mL of ethyl acetate was added, and the mixture was stirred at room temperature for 30 minutes. Then, 25 mL of water was added, and the mixture was separated. The aqueous layer was removed, and the organic layer was concentrated, and then hexane was added, followed by filtration and drying, to obtain 4.6 g (yield 90%) of 2,3,5-triiodobenzoic acid methyl ester. The product was confirmed by NMR and LC-MS. The molecular weight was 514.
• Example 11 Compound 10 (4) having a benzene core
• the esterification step of Example 1k was carried out under reflux conditions by placing 15 g of 2,3,5-triiodobenzoic acid, 150 mL of toluene, 20 g of methanol (20 equivalents), and 1.8 g of sulfuric acid (0.6 equivalents) in a vessel connected to a reflux tube. After 8 hours, 1.8 g of sulfuric acid (0.6 equivalents) was added and reacted for 16 hours. After cooling, the mixture was washed with 100 mL of water, 100 mL of 10% aqueous sodium carbonate solution was added, and the mixture was washed with 100 mL of water.
• Example 1m Compound 10 (5) having a benzene core The same procedure as in Example 1k was repeated except that lithium chloride was used instead of calcium chloride, to give 2.1 g of compound 10 (yield 55%).
• Example 1n Compound 10 (6) having a benzene core The same procedure as in Example 1k was carried out without using calcium chloride, and 2 mL of methanol was added to obtain 1.4 g of compound 10 (yield 40%).
• Example 1o Compound 10 (7) having a benzene core The same procedure as in Example 1k was carried out without using calcium chloride and using lithium aluminum hydride instead of sodium borohydride, to obtain 0.6 g of compound 10 (yield 15%).
• a 100 L glass-lined reaction vessel connected to a reflux tubing was charged with 700 g of 4-hydroxybenzaldehyde, 4900 ml of methanol, and 1260 ml of pure water, which were dissolved by stirring at 220 rpm for 1 hour under nitrogen flow. 1590 g of sodium bicarbonate was then gradually added in 10 portions over 10 minutes, followed by 3200 g of iodine, which was gradually added in 10 portions over 40 minutes. During this time, the liquid temperature rose to 47°C, and bubbling was observed. Stirring was continued for 8 hours while maintaining the internal temperature at 46°C using a hot water bath. An additional 300 g of iodine was added at the 5-hour mark.
• a 20 L separable flask was filled with ethanol (5 L) in an ice bath, and 2450 g of the protected product obtained in the previous step was gradually added and suspended. Under a nitrogen flow, 50 g of sodium borohydride was added in 5 g increments over 60 minutes while stirring. After stirring for 1 hour in an ice bath, 842 g of a 5% by mass aqueous solution of ammonium chloride was added dropwise over 15 minutes. Under ice cooling, the resulting reaction solution was gradually added to 21 L of pure water and stirred for 30 minutes. The precipitate that gradually formed during stirring was filtered off, and then rinsed with 5 L of pure water.
• the resulting precipitate was dissolved in 10.5 L of ethyl acetate, and washed three times with 3.5 L of a 10% by mass aqueous solution of NaCl. The resulting ethyl acetate solution was recovered, and 200 g of magnesium sulfate was added and suspended for 30 minutes. The filtrate obtained by filtration was concentrated to a concentration of about 50% by mass ⁇ 5%, and 9 L of heptane was added to perform crystallization. The filtered crystals were rinsed with cold heptane and then dried to obtain 1,680 g of compound (1-3) with a yield of 77% and LC purity of 99.8%. The product was confirmed by NMR and LC-MS. The molecular weight was 434.
• the [iodination step], [protective group introduction step], and [reduction step] were carried out in the same manner as in Synthesis Example L1, except that salicylaldehyde was used instead of 4-hydroxybenzaldehyde and the iodination step was changed to the iodination step L2 described below, to obtain compound (1-4).
• the formation was confirmed by NMR and LC-MS.
• the molecular weight changed from 432 to 434 before and after the reduction step.
• the obtained precipitate was dissolved in 10.5L of ethyl acetate, and then washed three times with 3.5L of a 10% by mass aqueous solution of NaCl.
• the obtained ethyl acetate solution was recovered, and then 200g of magnesium sulfate was added and suspended for 30 minutes.
• the filtrate obtained by filtration was concentrated to a concentration of about 50% by mass ⁇ 5%, and 9L of heptane was added to perform crystallization.
• the filtered crystallized product was further rinsed with cold heptane and then dried to obtain 1171 g of compound (1-7) with a yield of 77% and an LC purity of 99.8%.
• the product was confirmed by NMR and LC-MS.
• the molecular weight changed from 306 to 308 before and after the reduction step.
• a 20 L separable flask was filled with ethanol (5 L) in an ice bath, and 1,012 g of the above-mentioned protected substance BPL1P was gradually added and suspended. Under a nitrogen flow, 50 g of sodium borohydride was added in 5 g portions over 60 minutes while stirring. After stirring for 1 hour in an ice bath, 842 g of a 5% by mass aqueous solution of ammonium chloride was added dropwise over 15 minutes. Under ice cooling, the resulting reaction solution was gradually added to 21 L of pure water and stirred for 30 minutes. The precipitate that gradually formed during stirring was filtered off, and then rinsed with 5 L of pure water.
• the resulting precipitate was dissolved in 10.5 L of ethyl acetate, and washed three times with 3.5 L of a 10% by mass aqueous solution of NaCl. The resulting ethyl acetate solution was recovered, and 200 g of magnesium sulfate was added and suspended for 30 minutes. The filtrate obtained by filtration was concentrated to a concentration of about 50% by mass ⁇ 5%, and 9 L of heptane was added to perform crystallization. The filtered crystals were rinsed with cold heptane and then dried to obtain compound (BPL1R) (716 g) with a yield of 70% and a purity of 99.6%. The formation was confirmed by NMR and LC-MS. The molecular weight was 182.
• a 100L stainless steel reaction vessel connected to a reflux condenser was charged with 700g of 4-hydroxybenzaldehyde and 4900ml of methanol, which were dissolved by stirring at 220 rpm for 1 hour under nitrogen flow.
• the reaction vessel was cooled on ice, and an aqueous solution of sodium hydroxide prepared by dissolving 757g of sodium hydroxide in 1260mL of pure water was gradually added to the reaction vessel, after which 3200g of iodine was gradually added in 10 portions over 60 minutes.
• the mixture was stirred for 8 hours while maintaining the internal temperature at 60°C using a hot water bath.
• DML1D dehydrated dimethylformamide
• 380 g of diisopropylethylamine was added using a dropping funnel over 30 minutes while stirring in an ice bath, and stirred for an additional 60 minutes.
• 255 g of chloromethyl ethyl ether was added dropwise to the stirred reaction solution over 60 minutes using a dropping funnel, and stirred for an additional 30 minutes in an ice bath.
• a 20 L separable flask was filled with ethanol (5 L) in an ice bath, and 996 g of the prepared protected DML1P was gradually added and suspended. Under a nitrogen flow, 19 g of sodium borohydride was added in 3 g portions over 60 minutes while stirring. After stirring for 1 hour in an ice bath, 350 g of 5 wt. % aqueous ammonium chloride solution was added dropwise over 15 minutes. Under ice cooling, the resulting reaction solution was gradually added to 8 L of pure water and stirred for 30 minutes. The precipitate that gradually formed during stirring was filtered off, and then rinsed with 2 L of pure water.
• the resulting precipitate was dissolved in 4 L of ethyl acetate, and washed three times with 1.5 L of 10 wt. % aqueous NaCl solution. The resulting ethyl acetate solution was recovered, and 80 g of magnesium sulfate was added and suspended for 30 minutes. The filtrate obtained by filtration was concentrated to a concentration of about 50 wt. % ⁇ 5%, and 9 L of heptane was added to perform crystallization. The filtered crystals were further rinsed with cold heptane and then dried to obtain 701 g of compound DML1R with a yield of 70% and a purity of 99.2%. The formation was confirmed by NMR and LC-MS. The molecular weight was 614.
• DML2R was synthesized in the same manner as in Synthesis Example DML1, except that 4-hydroxybenzaldehyde was used as the raw material, the type of protecting agent was ethyl vinyl ether, and the [protecting group introduction step] was changed to the method described below. The formation was confirmed by NMR and LC-MS. The molecular weight was 642.
• washing treatment was performed with 7 L of 5% sodium bicarbonate water (once) and 7 L of ion-exchanged water (three times), after which 50 g of silica gel was added to perform silica gel dispersion, and the organic phase was recovered by filtration.
• a drive-out concentration 40°C was performed with n-heptane, and it was confirmed that there was no outflow of THF. Thereafter, a drive-out concentration was further performed using high-purity IPA (Kanto Chemical EL-IPA).
• Synthesis Example DML1e The compound (1-4) obtained in Synthesis Example L2 was used to carry out the [reduction step] of Synthesis Example L1 to obtain a compound (1-4a). The production was confirmed by NMR and LC-MS. The molecular weight was 376. In a 200 mL container connected to a reflux condenser, 5 g (13.3 mmol) of the obtained compound (1-4a) and 100 mL of toluene were placed and reacted under reflux conditions for 1 hour, and then separated by column chromatography to obtain 0.4 g (0.55 mmol) of compound 1-4b. The production was confirmed by NMR and LC-MS. The molecular weight was 734. Next, the compound 1-4b was used to carry out the [Protective Group Introduction Step] of Synthesis Example L1 to obtain a compound (DML1e). The production was confirmed by NMR and LC-MS. The molecular weight was 850.
• Example 2 Compound having naphthalene as a parent nucleus The compound was produced according to the following scheme: The reaction was carried out under a nitrogen stream.
• compound DMNa-2-1R was obtained in the same manner as in the synthesis of compound 1-3, except that compound DMNa2-1P was used instead of compound 1-2.
• the formation was confirmed by NMR and LC-MS.
• the molecular weight was 714.
• compound DMNa-3-1R was obtained in the same manner as in the synthesis of compound 1-3, except that compound DMNa3-1P was used instead of compound 1-2.
• the formation was confirmed by NMR and LC-MS.
• the molecular weight was 714.
• compound DMNa-2b-1R was obtained in the same manner as in the reduction step DML1R, except that compound DMNa-2b-1P was used instead of DML1P.
• the formation was confirmed by NMR and LC-MS. The molecular weight was 714.
• a flask equipped with a stirrer and a cooling tube was immersed in an oil bath, and 80 g of compound 3-1 (manufactured by Mitsubishi Gas Chemical Company, Inc., 0.43 mol) and 2.5 L of toluene were charged into the flask and stirred.
• 400 g (1.72 mol) of 55% aqueous hydrogen iodide solution was added to the flask.
• the internal temperature was set to 83-89°C and the reaction was carried out for 32 hours.
• 50 g of 55% aqueous hydrogen iodide solution was added to the flask.
• the internal temperature was set to 83-89°C and the reaction was carried out for 16 hours.
• the organic phase was filtered and washed with chilled toluene and hexane to obtain 145 g of a wet cake.
• the wet cake was dried under reduced pressure at 40°C for 2.5 hours to obtain 138 g of pale red crystals.
• the crystals were then mixed with 1.3 L of ethyl acetate and dissolved by heating to 70°C.
• the ethyl acetate solution was cooled to room temperature. 650 mL of 0.5% aqueous sodium sulfite solution was added to the liquid, stirred, separated, and the ethyl acetate phase was removed.
• reaction solution was filtered to separate the toluene solution and 12 g of crystals, and the toluene solution was washed five times with 29 g of water to obtain 85 g of toluene solution.
• 28 g of water and 0.4 g of 10% aqueous sodium sulfite solution were added and washed.
• six separate washings were performed with 85 g of water to obtain 105 g of ethyl acetate solution.
• a flask equipped with a reflux condenser and a Dean-Stark tube was immersed in an oil bath, and 80 g of compound 3-1 (manufactured by Mitsubishi Gas Chemical Company, Inc., 0.43 mol) and 2.5 L of o-xylene were charged into the flask and stirred.
• 80 g of compound 3-1 manufactured by Mitsubishi Gas Chemical Company, Inc., 0.43 mol
• 2.5 L of o-xylene 2.5 L
• 400 g (1.72 mol) of 55% aqueous hydrogen iodide solution was added to the flask.
• the internal temperature was set to 125°C and the reaction was carried out for 3 hours. After that, the mixture was stirred for 1 hour in a 25°C water bath.
• a flask equipped with a reflux condenser and a Dean-Stark tube was immersed in an oil bath, and 87.9 g of compound Ad-2-1 (0.43 mol) and 2.5 L of toluene were charged into the flask and stirred.
• 400 g (1.72 mol) of 55% aqueous hydrogen iodide solution was added to the flask.
• the internal temperature was set to 100°C and the reaction was carried out for 3 hours. After that, the mixture was stirred for 1 hour in a water bath at 25°C.
• DMA3-2 was obtained in the same manner as in the synthesis of Ad-A-3-2, except that 60 g (258 mmol) of 55% aqueous hydrogen iodide solution was used instead of 18 mL (289 mmol) of iodomethane.
• DMA3a was obtained in the same manner as in the synthesis of Ad-A-3, using DMA3-2 instead of AdA-3-2.
• the production was confirmed by NMR and LC-MS. The molecular weight was 626.
• DMA4a was obtained in the same manner as Ad-A-4, except that DMA3a was used instead of AdA-3. The formation was confirmed by NMR and LC-MS. The molecular weight was 598.
• DAMA1-mx was obtained in the same manner as in the synthesis of DAMA1-tl, except that meta-xylene was used instead of toluene. The production was confirmed by NMR and LC-MS. The molecular weight was 398.
• DAMA1-eb was obtained in the same manner as in the synthesis of DAMA1-tl, except that ethylbenzene was used instead of toluene. The production was confirmed by NMR and LC-MS. The molecular weight was 398.
• the weight average molecular weight (Mw) of this polymer was 11,500, and the dispersity (Mw/Mn) was 1.90.
• the following formula (MAR) is written simply to show the ratio of each structural unit, but the order of the structural units is random, and it is not a block copolymer in which each structural unit forms an independent block.
• the molar ratio was calculated based on the integral ratio of the main chain carbon directly bonded to benzene for the unit having benzene, and the carbonyl carbon of the ester bond for the methacrylate-based units (2-methyl-2-adamantyl methacrylate, ⁇ -butyrolactone methacrylate, and hydroxyadamantyl methacrylate).
• compositions shown in Table 1 were prepared using compound 1-3 synthesized in Example 1, compound 2-3 and compound 2-4 synthesized in Example 2, compound 3-2 synthesized in Example 3, compound 8 synthesized in Example 1g, compound 9 synthesized in Example 1h, and compound 10 synthesized in Example 1i as compound B.
• acid generators Triphenylsulfonium nonafluorobutanesulfonate (TPS-109) manufactured by Midori Chemical Co., Ltd.
• Acid diffusion control agent Tri-n-octylamine (TOA) manufactured by Kanto Chemical
• Kanto Chemical Organic solvent Propylene glycol monomethyl ether acetate (PGMEA) manufactured by Kanto Chemical
• Example 8 to 11 EUV exposure sensitivity, etching defects (EUV exposure sensitivity)
• the compositions prepared in Examples 4 to 7 and 7A to 7C were spin-coated on a silicon wafer, and then baked at 110° C. for 60 seconds to form a photoresist layer with a thickness of 100 nm.
• compound 3-1 was used instead of compound 1-3 in Example 4.
• EUV extreme ultraviolet
• EUVES-7000 product name, manufactured by LithoTech Japan Co., Ltd.
• PEB baking
• TMAH tetramethylammonium hydroxide
• the film thickness was measured using an optical interference film thickness meter "VM3200" (product name, manufactured by SCREEN Semiconductor Solutions Co., Ltd.) to obtain profile data of film thickness versus exposure dose.
• the exposure dose at which the slope of the film thickness variation versus exposure dose was greatest was calculated as the sensitivity value (mJ/ cm2 ), which was used as an index of the EUV sensitivity of the resist.
• the composition used in the EUV exposure sensitivity measurement was applied onto an 8-inch silicon wafer having an oxide film with a thickness of 100 nm formed on the outermost surface, and baked at 110° C. for 60 seconds to form a photoresist layer with a thickness of 100 nm.
• EUV extreme ultraviolet
• EUVES-7000 product name, manufactured by LithoTech Japan Co., Ltd.
• shot exposure was performed on the entire surface of the wafer at an exposure amount 10% less than the EUV sensitivity value obtained in the above-mentioned EUV sensitivity evaluation, and further baked (PEB) at 110° C. for 90 seconds and developed with a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds to obtain a wafer that had been shot-exposed for 80 shots on the entire surface of the wafer.
• EUV extreme ultraviolet
• EUVES-7000 product name, manufactured by LithoTech Japan Co., Ltd.
• Example 12 Acid-purified product of compound 3-2 (Treatment 1: Acid-purified product)
• a solution (10% by mass) in which compound 3-2 was dissolved in PGMEA was charged, and heated to 80 ° C. while stirring.
• 37.5 g of an aqueous oxalic acid solution (pH 1.3) was added, stirred for 5 minutes, and then allowed to stand for 30 minutes.
• the oil phase and the aqueous phase were separated, and the aqueous phase was removed.
• the metal contents of a 10% by mass PGMEA solution of compound 3-2 that had not been treated, a 10% by mass PGMEA solution of compound 3-2 that had been treated with treatment 1, and a 10% by mass PGMEA solution of compound 3-2 that had been treated with treatment 2 were measured by ICP-MS. The measurement results are shown in the table below.
• the purified compound 3-2 was used to measure EUV exposure sensitivity and etching defects in the same manner as in Example 8. The measurement results are shown in the following table.
• the filtered material was placed in a container equipped with a stirrer, 500 mL of methanol was added, and the mixture was stirred for 15 minutes.
• the precipitate was filtered and washed with 150 mL of methanol.
• the precipitate was separated using column chromatography (Kanto Chemical spherical silica 60N) with a gradient of ethyl acetate:hexane as the developing solvent at a ratio of 1:9 to 9:1, yielding compounds 1-1, 1-1a, and 1-1b in a relative ratio of approximately 1:0.9:0.5.
• the molecular weights of each component of the mixture were measured by LC-MS, giving compound 1-1 at 374, compound 1-1a at 248, and compound 1-1b at 494.
• Example 14 to 18 Evaluation of EUV exposure sensitivity and etching defects Compositions were prepared in the same manner as in Example 4, using the following compounds as compound B. The mass ratios of each compound contained in the composition are shown in the table. EUV exposure sensitivity and etching defects were evaluated in the same manner as in Example 8. However, etching defects were evaluated according to the following criteria. (Evaluation Criteria) S: Number of cone defects ⁇ 6 A': 6 ⁇ Number of cone defects ⁇ 10 B: 10 ⁇ Number of cone defects ⁇ 80 C: 80 ⁇ Number of cone defects ⁇ 400 D: 400 ⁇ Number of cone defects
• the resulting BPL1Pc was used as the raw material to obtain BPL1c in the same manner as in the reduction process BPL1R.
• the formation was confirmed by NMR and LC-MS.
• the molecular weight was 196.
• Example L1 (Synthesis Example Na-0b) In Example L1, the [protecting group introduction step] was carried out using 6-hydroxy-2-naphthaldehyde instead of 4-hydroxy-3,5-diiodobenzaldehyde, followed by the [reduction step] to obtain compound Na-0b. The production was confirmed by NMR and LC-MS. The molecular weight was 232.
• Example L1 (Synthesis Example Na-2b)
• the [protective group introduction step] was carried out using 2-hydroxy-1-naphthaldehyde instead of 4-hydroxy-3,5-diiodobenzaldehyde, followed by the [reduction step] to obtain compound Na-2b.
• the production was confirmed by NMR and LC-MS.
• the molecular weight was 232.
• Ad-A-2b was obtained in the same manner as Ad-A-2, except that 1,3,5-adamantanetriol was used instead of 1-iodoadamantane-3,5-diol. The formation was confirmed by NMR and LC-MS. The molecular weight was 414.
• Ad-A-2c was obtained in the same manner as in the synthesis of Ad-2-3, except that 1,3,5-adamantanetriol was used instead of Ad-2-2. The production was confirmed by NMR and LC-MS. The molecular weight was 540.
• Ad-A-2d was obtained in the same manner as in the synthesis of Ad-2-4, except that 1,3,5-adamantanetriol was used instead of Ad-2-2. The production was confirmed by NMR and LC-MS. The molecular weight was 484.
• Ad-2-3b was obtained in the same manner as in the synthesis of Ad-A-2, except that 1,3,5,7-adamantanetetraol was used instead of Ad-A-1. The formation was confirmed by NMR and LC-MS. The molecular weight was 506.
• the compound of this embodiment has industrial applicability, for example, in providing a lithography composition that is highly sensitive and has few defects when exposed to EUV light while maintaining good pattern shape.
• Example 19-1 Evaluation was performed in the same manner as in Examples 4 and 8, except that compound B shown in the table below was used instead of compound 1-3 shown in Example 14, and the evaluation conditions were changed to a post-exposure bake temperature of 100° C. for 120 seconds. As a result, as shown in the table below, good evaluation results were confirmed for both the resist pattern and EUV exposure sensitivity, similar to Examples 4 and 8.
• Example 19-2 Evaluation was performed in the same manner as in Examples 4 and 8, except that compound B1 shown in the table below was used instead of compound 1-3 shown in Example 14, and the evaluation conditions were changed to a post-exposure bake temperature of 100° C. for 120 seconds. As a result, as shown in the table below, good evaluation results were confirmed for both the resist pattern and EUV exposure sensitivity, similar to Examples 4 and 8.
• Example 20-1 The EUV sensitivity and etching defects were evaluated in the same manner as in Examples 14 to 18, except that compounds B1 and B2 shown in the table below were used in the ratios shown below instead of compounds 1-3 and 1-3a.
• Example 20-2 The EUV sensitivity and etching defects were evaluated in the same manner as in Examples 14 to 18, except that compounds B1 and B2 shown in the table below were used in the ratios shown below instead of compounds 1-3 and 1-3a.
• Example 21 Except for using the compounds shown in the table below instead of compound 3-2, compounds subjected to treatment 1 or treatment 2 were obtained in the same manner as in Example 12, and the EUV sensitivity and etching defects were evaluated. As a result, as in Example 12, good results were confirmed for EUV sensitivity and etching defects for all compounds.
• Example 22 The following compositions were prepared according to the method of Example 4. (Values: parts by weight)
• the composition was subjected to a time-lapse test under the following conditions, and the state of the solution after the test was evaluated based on the absorbance using a spectrophotometer. Specifically, the spectrum in the visible light region of the sample after the time-lapse test was measured to determine the "average absorbance A1 at 450 nm, 550 nm, and 650 nm," and the difference ⁇ A from the "average absorbance A0 at 450 nm, 550 nm, and 650 nm" before the start of the test was calculated and evaluated.
• ⁇ A A1 - A0
• Example 23 The following compositions were prepared according to the method of Example 4 (values: parts by mass). The temporal stability of the compositions was evaluated in the same manner as in Example 22.
• Example 24 The following compositions were prepared according to the method of Example 4 (values: parts by mass). The temporal stability of the compositions was evaluated in the same manner as in Example 22.
• compositions were prepared according to the method of Example 4 (values: parts by mass).
• stability of the compositions over time was evaluated using the same method as in Example 22.
• Example 26 The following compositions were prepared according to the method of Example 4 (values: parts by mass). The temporal stability of the compositions was evaluated in the same manner as in Example 22.
• Example 27 The following compositions were prepared according to the method of Example 4 (values: parts by mass). The temporal stability of the compositions was evaluated in the same manner as in Example 22.
• Example 28 A time-course test was carried out in the same manner as in Example 22, except that Compound B1 and Compound B2 in Example 22 were changed to the compounds shown in the table below. As a result, it was found that, in any of the compositions, the increase in absorbance in the spectroscopic spectrum after the time-course test was suppressed by using a predetermined amount of Compound B2 in combination, as in Example 22.
• Example 23 A time-course test was conducted in the same manner as in Example 23, except that compound B1 and compound B2 in Example 23 were changed to the compounds listed in the table below. As a result, it was found that in both compositions, as in Example 23, the increase in absorbance in the spectroscopic spectrum after the time-course test was suppressed by using a specified amount of compound B2 in combination.
• Example 29 A time-course test was carried out in the same manner as in Example 22, except that Compound B1 and Compound B2 in Example 22 were changed to the compounds shown in the table below. As a result, it was found that, in any of the compositions, the increase in absorbance in the spectroscopic spectrum after the time-course test was suppressed by using a predetermined amount of Compound B2 in combination, as in Example 22.
• Example 23 A time-course test was conducted in the same manner as in Example 23, except that compound B1 and compound B2 in Example 23 were changed to the compounds listed in the table below. As a result, it was found that in both compositions, as in Example 23, the increase in absorbance in the spectroscopic spectrum after the time-course test was suppressed by using a specified amount of compound B2 in combination.

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