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WO2011111762A1 - Procédé de production d'un dérivé de diaryle, nouveau dérivé de binaphtyle, procédé de production d'un dérivé d'arène et nouveau dérivé d'arène - Google Patents

Procédé de production d'un dérivé de diaryle, nouveau dérivé de binaphtyle, procédé de production d'un dérivé d'arène et nouveau dérivé d'arène Download PDF

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WO2011111762A1
WO2011111762A1 PCT/JP2011/055578 JP2011055578W WO2011111762A1 WO 2011111762 A1 WO2011111762 A1 WO 2011111762A1 JP 2011055578 W JP2011055578 W JP 2011055578W WO 2011111762 A1 WO2011111762 A1 WO 2011111762A1
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binaphthyl
derivative
sulfonyl
oxy
trifluoromethyl
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豊司 嶋田
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Daicel Corp
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Daicel Chemical Industries Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
    • C07C309/63—Esters of sulfonic acids
    • C07C309/64—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms
    • C07C309/65—Esters of sulfonic acids having sulfur atoms of esterified sulfo groups bound to acyclic carbon atoms of a saturated carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/26—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids
    • C07C303/30—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfonic acids by reactions not involving the formation of esterified sulfo groups

Definitions

  • the present invention relates to a method for producing a diaryl derivative and a novel binaphthyl derivative, a method for producing an arene derivative, and a novel arene derivative.
  • the binaphthyl derivative having a relatively bulky substituent at the 2,2′-position has axial asymmetry derived from the 1,1′-binaphthyl structure.
  • a binaphthyl derivative for example, 2,2'-bis (diphenylphosphino) -1,1'-binaphthyl (BINAP) is known. It is known that BINAP can be used as an asymmetric ligand in asymmetric synthesis.
  • binaphthyl derivative for example, diiodo BINAP in which iodine is introduced into the 5,5′-position of binaphthyl is known, and furthermore, this diiodo BINAP is known to be obtained efficiently by using diiodohydantoin. (See, for example, Non-Patent Document 1).
  • binaphthyl derivatives having an asymmetric structure such as BINAP and diiodo BINAP described above is expected to bring about improvement and establishment of technology by asymmetric identification, and is expected in the technical field using asymmetric identification. Has been.
  • the present invention provides a method capable of producing a diaryl derivative having an asymmetric structure and a novel binaphthyl derivative.
  • the present invention provides a method and a novel arene derivative capable of performing iodination and trifluoromethanesulfonyloxylation in a single reaction step in a specific arene.
  • the inventors of the present invention reacted with a specific binaphthyl derivative having an asymmetric structure with trifluoromethanesulfonic acid in the presence of diiodohydantoin, so that the asymmetric structure was maintained and the binaphthyl was high at the 4,4 ′ position.
  • the inventors have found that a (trifluoromethyl) sulfonyl] oxy group can be introduced with selectivity, thereby completing the present invention.
  • the present invention relates to S or R form of 2,2′-diformyl-1,1′-diaryl trifluoromethanesulfonic acid or a mixture thereof in the presence of N, N′-diiodo-5,5-dimethylhydantoin.
  • S form or R form of 4,4′-bis [[(trifluoromethyl) sulfonyl] oxy] -2,2′-diformyl-1,1′-diaryl or a mixture thereof Provided is a process for producing 4′-bis [[(trifluoromethyl) sulfonyl] oxy] -2,2′-diformyl-1,1′-diaryl.
  • the present invention also relates to S- or R-form of 2,2'-diformyl-1,1'-diaryl trifluoromethanesulfonic acid or a mixture thereof in the presence of N, N'-diiodo-5,5-dimethylhydantoin.
  • the present invention also provides the above production method, wherein the diaryl is binaphthyl.
  • the present invention also provides 4,4′-bis [[(trifluoromethyl) sulfonyl] oxy] -2,2′-diformyl-1,1′-binaphthyl in the S form or R form or a mixture thereof.
  • the present invention is also obtained by reacting the formyl group of S-form or R-form of 4,4′-bis [[(trifluoromethyl) sulfonyl] oxy] -2,2′-diformyl-1,1′-binaphthyl. 4,4′-bis [[(trifluoromethyl) sulfonyl] oxy] -1,1′-binaphthyl derivatives of S form or R form or a mixture thereof.
  • the present invention also relates to an S form or R form of 4,4′-bis [[(trifluoromethyl) sulfonyl] oxy] -2,2′-bis (hydroxymethyl) -1,1′-binaphthyl or a mixture thereof.
  • 4,4′-bis [[(trifluoromethyl) sulfonyl] oxy] -1,1′-binaphthyl derivatives of the S form or R form or a mixture thereof are provided.
  • iodination and trifluoromethylsulfonyloxylation of formylarene are carried out by reacting diiodohydantoin and trifluoromethanesulfonic acid with formylarene.
  • the present invention relates to the reaction of N, N′-diiodo-5,5-dimethylhydantoin and trifluoromethanesulfonic acid with formylarene to obtain iodinated [[(trifluoromethyl) sulfonyl] oxy] formylarene. Further provided is a process for preparing [[(trifluoromethyl) sulfonyl] oxy] formylarene.
  • the present invention also provides a process for producing the above [[(trifluoromethyl) sulfonyl] oxy] formylarene iodide, wherein the formylarene is 2-naphthaldehyde.
  • the present invention provides 3-trifluoromethylsulfonyloxy-5,7,8-triiodo-2-naphthaldehyde.
  • a novel binaphthyl derivative having a [(trifluoromethyl) sulfonyl] oxy group introduced at the 4,4′-position of binaphthyl can be provided.
  • the present invention can provide a formylarene iodide and a trifluoromethanesulfonyloxy compound in one reaction step, and can provide a novel formylarene derivative into which iodine and a trifluoromethanesulfonyloxy group are introduced. .
  • FIG. 3 is a diagram showing a 1 H NMR spectrum of (S) -4,4′-bis [[(trifluoromethyl) sulfonyl] oxy] -2,2′-diformyl-1,1′-binaphthyl obtained in Example 1. It is. Part of the 1 H NMR spectrum of (S) -4,4′-bis [[(trifluoromethyl) sulfonyl] oxy] -2,2′-diformyl-1,1′-binaphthyl obtained in Example 1 It is a figure which expands and shows.
  • FIG. 3 is a diagram showing a 1 H NMR spectrum of (S) -4,4′-bis [[(trifluoromethyl) sulfonyl] oxy] -2,2′-diformyl-1,1′-binaphthyl obtained in Example 1. It is. Part of the 1 H NMR spectrum of (S) -4,4′-bis [[(tri
  • FIG. 1 represents the 1 H NMR spectrum of (S) -4,4′-bis [[(trifluoromethyl) sulfonyl] oxy] -2,2′-dicarboxyl-1,1′-binaphthyl obtained in Example 1.
  • FIG. 13 represents the 13 C NMR spectrum of (S) -4,4′-bis [[(trifluoromethyl) sulfonyl] oxy] -2,2′-dicarboxyl-1,1′-binaphthyl obtained in Example 1.
  • FIG. 3 is a diagram showing the results of X-ray crystal structure analysis of the product obtained in Example 2.
  • the present invention relates to an S form or R form of 4,4′-bis [[(trifluoromethyl) sulfonyl] oxy] -2,2′-diformyl-1,1′-diaryl or a mixture thereof (hereinafter referred to as “di- Also referred to as “triflate diformyl diaryl”) and derivatives thereof which are S-form or R-form or mixtures thereof.
  • ditriflate diformyl diaryl refers to a diaryl in which a group derived from a formyl group is introduced into one or both of the 2,2 ′ positions of ditriflate diformyl diaryl (hereinafter referred to as “ditriflate diaryl”). Also referred to as a “derivative”).
  • diaryl is a compound in which two aromatic rings are bonded to each other at the 1,1'-position by a single bond.
  • the two aromatic groups in diaryl are not particularly limited as long as they have a formyl group at the 2,2 ′ position, and may be the same or different.
  • the aromatic group in diaryl preferably has 6 to 18 carbon atoms.
  • An example of such diaryl is binaphthyl.
  • the present invention will be described by taking binaphthyl as an example.
  • the S form or R form of 4,4′-bis [[(trifluoromethyl) sulfonyl] oxy] -2,2′-diformyl-1,1′-binaphthyl or a mixture thereof is referred to as “ditriflate. It is also called “diformyl binaphthyl”.
  • a derivative of ditriflate diformylbinaphthyl which is S form or R form or a mixture thereof is also referred to as “ditriflate binaphthyl derivative”.
  • Ditriflate diformylbinaphthyl reacts with S or R form of 2,2'-diformyl-1,1'-binaphthyl with trifluoromethanesulfonic acid in the presence of N, N'-diiodo-5,5-dimethylhydantoin To obtain.
  • the starting material 2,2′-diformyl-1,1′-binaphthyl may be S-form, R-form, or a mixture thereof. From the viewpoint of use, it is preferable that it is S body or R body.
  • 2,2′-Diformyl-1,1′-binaphthyl is, for example, ditriflated from 2,2′-dihydroxy-1,1′-binaphthyl (binaphthol), followed by palladium catalysis in the presence of carbon monoxide. It can be obtained by carboxymethylation and reduction of the resulting 2,2′-bis (carboxymethyl) -1,1′-binaphthyl. In this method, the axial asymmetry of the raw material is maintained up to the product.
  • the amount of N, N′-diiodo-5,5-dimethylhydantoin used in the synthesis of ditriflate diformylbinaphthyl is 2,2′-diformyl-1,1 ′ from the viewpoint of increasing the yield of ditriflate diformylbinaphthyl.
  • -It is preferably at least 2 molar equivalents relative to binaphthyl, more preferably at least 3 molar equivalents.
  • the amount of N, N′-diiodo-5,5-dimethylhydantoin used is 5 molar equivalents or less relative to 2,2′-diformyl-1,1′-binaphthyl. It is preferable that it is 3.5 mol equivalent or less.
  • N, N′-diiodo-5,5-dimethylhydantoin can be converted into iodine monochloride in 5,5-dimethylhydantoin in the presence of a base in an aqueous solution, as described in, for example, WO 2007/026766. Can be obtained by reacting.
  • the amount of trifluoromethanesulfonic acid used in the synthesis of ditriflate diformylbinaphthyl is at least 2 molar equivalents relative to 2,2′-diformyl-1,1′-binaphthyl from the viewpoint of increasing the yield of ditriflate diformylbinaphthyl. It is preferable that it is 4 mol equivalent or more. From the standpoint of the effect and economical viewpoint, the amount of trifluoromethanesulfonic acid used is preferably 10 molar equivalents or less, preferably 7 molar equivalents relative to 2,2′-diformyl-1,1′-binaphthyl. The following is more preferable. Trifluoromethanesulfonic acid can be obtained as a commercial product.
  • the synthesis of ditriflate diformyl binaphthyl can be performed in a solvent.
  • the solvent may be one type or two or more types.
  • a solvent inert to the synthesis of the above-mentioned ditriflate diformylbinaphthyl can be used, for example, halogen solvents such as dichloromethane, dichloroethane, chloroform, and carbon tetrachloride, THF, And ether solvents such as dioxane, cyclopentyl methyl ether (CPME), and methyl tertiary butyl ether (MTBE).
  • the solvent can be selected according to the reaction conditions. For example, when heating is required, since dichloromethane has a low boiling point, it is preferable to use dichloroethane rather than dichloromethane.
  • the synthesis reaction of ditriflate diformylbinaphthyl can be carried out in the range of 0 to 80 ° C.
  • the reaction temperature in the synthesis of ditriflate diformylbinaphthyl is 0 to 50 ° C. from the viewpoint of preventing the decomposition of N, N′-diiodo-5,5-dimethylhydantoin and suppressing the formation of by-products. It is preferably 20 to 40 ° C.
  • the synthesis of ditriflate diformylbinaphthyl is preferably performed in a dry nitrogen atmosphere from the viewpoint of preventing the deterioration of trifluoromethanesulfonic acid.
  • the product is preferably recovered from the reaction solvent and purified using ordinary techniques such as column chromatography and recrystallization. However, when the reaction or treatment is continued, Recovery and purification from the reaction solvent may be omitted.
  • the ditriflate binaphthyl derivative is prepared by reacting the formyl group of the ditriflate diformylbinaphthyl with a group other than the formyl group derived from the formyl group at one or both of the 2,2 ′ positions of the ditriflate diformylbinaphthyl. It is obtained by introducing. Groups other than the formyl group can be introduced directly from the formyl group or by ordinary techniques of organic synthesis in which other groups are formed through two or more steps.
  • ditriflate binaphthyl derivative examples include a ditriflate binaphthyl derivative A having a group derived from a formyl group independently at one or both of the 2,2 ′ positions of binaphthyl, or a binaphthyl derivative derived from two formyl groups. And ditriflate binaphthyl derivative B having a cyclic group containing the 2,2′-position.
  • the ditriflate binaphthyl derivative A may have a group other than the formyl group only at one of the 2,2′-positions of binaphthyl, or both. Further, in the ditriflate binaphthyl derivative A, both groups at the 2,2′-position of binaphthyl may be the same or different. From the viewpoint of the use of optical resolution, it is preferable that the ditriflate binaphthyl derivative A has either the same group at the 2,2′-position or both of them.
  • Examples of the group other than the formyl group in the ditriflate binaphthyl derivative A include various groups derived from the formyl group directly or through two or more steps in normal organic synthesis. Examples of such groups include hydroxyalkyl groups, carboxyl groups, alkoxyl groups, imino groups, alkyl groups, alkenyl groups, amino groups, aminoalkyl groups, haloalkyl groups, alkynyl groups, alkylsilyl groups, alkenylsilyl groups, alkynyls.
  • Examples thereof include a silyl group, a phosphonyl group, a phosphinyl group, a sulfonyl group, a sulfinyl group, an acyl group, a ketene group represented by the following formula (1), and an allene group represented by the following formula (2).
  • the number of carbon atoms of alkoxyl, alkyl, alkenyl and alkynyl in the above group is preferably 20 or less, more preferably 1 to 12 (alkenyl and alkynyl are 2 to 12).
  • the group derived from the formyl group may contain 6 or less aromatic rings or heteroaromatic rings as a substituent. These aromatic groups preferably have 16 or less carbon atoms, more preferably 6 to 10 carbon atoms.
  • R independently represents hydrogen, a methyl group, or a phenyl group.
  • the ditriflate binaphthyl derivative B has a ring structure in which each of the 2,2′-positions of binaphthyl which is a formyl group or a group other than the formyl group is bonded by a ring-closing reaction such as dehydration condensation.
  • a ring structure examples include a 5- to 7-membered ring structure which may contain a hetero atom, for example, a ring containing a diol obtained by pinacol coupling of a formyl group of ditriflate diformylbinaphthyl, and Examples thereof include heterocyclic amines having an oxazolyl ring formed by a ring-closing reaction of amide obtained by condensation of formyl group and amino alcohol by treatment with triphenylphosphine in the presence of triethylamine.
  • ditriflate binaphthyl derivative examples include (S) or (R) -4,4′-bis [[(trifluoromethyl) sulfonyl] oxy] -2,2′-bis (hydroxymethyl) -1,1.
  • the ditriflate diformylbinaphthyl and the ditriflate binaphthyl derivative can be confirmed by a usual analyzer such as 1 H NMR, 13 C NMR, IR, MS.
  • the ditriflate diformylbinaphthyl and the ditriflate binaphthyl derivative are expected to be used as an asymmetry discrimination agent as they are.
  • ditriflate diformylbinaphthyl and the ditriflate binaphthyl derivative may be prepared by directly or through two or more steps of one or both of the 4,4′-position [(trifluoromethyl) sulfonyl] oxy groups. By replacing it with other groups such as phenyl group, naphthyl group, diphenylphosphonyl group and the like, further binaphthyl derivatives are expected to be used as asymmetric discriminating agents with improved asymmetric discrimination ability.
  • the Sonogashira reaction proceeds easily with binaphthyl iodide, and the trifluoromethylsulfonyl group has a cross-coupling activity equivalent to iodine. It is expected to be carried out by a head reaction, and such a reaction is expected to introduce, for example, a group having a carbon-carbon triple bond at the 4,4 ′ position of binaphthyl.
  • introduction of another group (for example, a phenol group) at the 4,4′-position can be performed by hydrolysis of a trifluoromethylsulfonyl group.
  • the ditriflate diformylbinaphthyl and the ditriflate binaphthyl derivative may be formed by removing hydrogen other than the 1,1 ′, 2,2 ′, and 4,4 ′ positions, for example, trimethylsilyl group, phenyl group, naphthyl group, diphenylphosphonyl.
  • replacement of hydrogen other than the 1,1 ′, 2,2 ′, and 4,4 ′ positions can be performed using known techniques. For example, replacement of the hydrogen at the 3,3 ′ position is performed by Chemistry Letters (2001). , (5), 386-387. Can be carried out according to the method described in the above, that is, the C—H activation reaction using a ruthenium catalyst.
  • the ditriflate diformylbinaphthyl and the ditriflate binaphthyl derivative have a [(trifluoromethyl) sulfonyl] oxy group at the 4,4 ′ position, for example, vinyl, allyl, ethynyl, propargyl, acryloyl, styryl, alkoxysilyl, By substituting with a polymerizable substituent such as allylsilyl, formation of a multimer having asymmetric discrimination ability is expected.
  • the ditriflate binaphthyl derivative is expected to form a multimer having asymmetric discrimination ability by adopting a polymerizable group as a group derived from a formyl group.
  • These multimers are expected to be used as a separating agent for optical isomers having a desired shape such as a particulate shape or a cylindrical shape.
  • Introduction of a polymerizable substituent into the ditriflate diformylbinaphthyl and the ditriflate binaphthyl derivative can be performed in the same manner as the introduction of other groups described above.
  • the ditriflate diformyl binaphthyl and the ditriflate binaphthyl derivative may be prepared by introducing a group having a binding property with a carrier such as an amino group, a hydroxyl group, and an epoxy group at any of the above-described positions.
  • a carrier such as an amino group, a hydroxyl group, and an epoxy group at any of the above-described positions.
  • the formation of a separating agent for optical isomers comprising a particulate or columnar carrier that can be used in liquid chromatography and the ditriflate diformylbinaphthyl or the ditriflate binaphthyl derivative supported on the carrier is expected. Is done.
  • the introduction of the group having the binding property can be carried out in the same manner as the introduction of the group described above into the ditriflate diformylbinaphthyl or the ditriflate binaphthyl derivative.
  • the present invention has been described above by taking binaphthyl as an example, but the production method of the present invention uses a diaryl derivative in which the above-mentioned binaphthyl is replaced with another diaryl, for example, biphenyl, bianthracene, bitetracene, biphenanthrene, bipyrene, or biclicene. Therefore, it is expected to be applied to the production of a diaryl derivative similar to the binaphthyl derivative.
  • N, N′-diiodo-5,5-dimethylhydantoin and trifluoromethanesulfonic acid are reacted with formylarene (hereinafter also referred to as “reaction B”) [[(trifluoromethyl) sulfonyl iodide]. ]
  • Oxy] formylarenes are provided.
  • the formylarene has one formyl group.
  • the carbon number of arene in formylarene is preferably 6-60.
  • Such arenes such as benzene, naphthalene, anthracene, phenanthrene, tetracene, pyrene, chrysene, tetracene, and C 60 fullerene and the like.
  • Examples of the formylarene include 2-naphthaldehyde, 2-formylanthracene, 9-formylanthracene, 2-formylpyrene, phthalaldehyde, and terephthalaldehyde.
  • the amount of N, N′-diiodo-5,5-dimethylhydantoin used in the reaction B can be determined according to the number of iodine introduced into the formylarene, and is 1.0 to 4. 0 is preferable, 2.0 to 4.0 is more preferable, and 3.5 to 4.0 is still more preferable.
  • the amount of trifluoromethanesulfonic acid used in reaction B can be determined according to the number of trifluoromethanesulfonyloxy groups to be introduced into formylarene, and the molar ratio with respect to formylarene is 2.0 to 8.0. It is preferably 4.0 to 8.0, more preferably 7.0 to 8.0.
  • the reaction temperature in the reaction B can be determined from the viewpoint of reactivity, and is preferably 25 to 40 ° C.
  • the reaction temperature in reaction B is preferably the boiling point of the reaction solvent from the viewpoint of easy control of the reaction temperature.
  • Reaction B can be carried out in the above-mentioned solvent in the same manner as the synthesis of ditriflate diformylbinaphthyl described above.
  • a solvent having a boiling point within the above reaction temperature range (for example, dichloromethane (boiling point: 40 ° C.)) is preferably used as the reaction solvent for reaction B.
  • reaction B is preferably performed in a dry nitrogen atmosphere from the viewpoint of preventing the deterioration of trifluoromethanesulfonic acid.
  • the product is preferably recovered from the reaction solvent and purified using ordinary techniques such as column chromatography and recrystallization. However, when the reaction or treatment is subsequently performed, the product is recovered from the reaction solvent. And purification may be omitted.
  • Reaction B for example, 3-trifluoromethylsulfonyloxy-5,7,8-triiodo-2-naphthaldehyde can be obtained from 2-naphthaldehyde by a one-step reaction.
  • the product of reaction B should be confirmed by using a refined product if necessary and using a device that performs normal analysis such as 1 H NMR, 13 C NMR, IR, MS, and X-ray crystal structure analysis. Can do.
  • the [[((trifluoromethyl) sulfonyl] oxy] formylarene iodide produced in the reaction B can be converted into various naphthalene aldehyde derivatives by performing derivatization using a cross-coupling reaction at the iodine and triflate positions as necessary. Is expected to be used in the synthesis of
  • the [[(trifluoromethyl) sulfonyl] oxy] formylarene iodide can be converted into a diaryl derivative by performing a homocoupling reaction as it is or through further derivatization.
  • the [[(trifluoromethyl) sulfonyl] oxy] formylarene iodide in this homocoupling reaction may be the same or different.
  • Examples of the derivatization of iodinated [[(trifluoromethyl) sulfonyl] oxy] formylarene include hydroxylation of a trifluoromethylsulfonyloxy group. Such hydroxylation can be performed by alkali hydrolysis of [[(trifluoromethyl) sulfonyl] oxy] formylarene iodide.
  • a diaryl derivative (homocoupled product) by homocoupling can be obtained, for example, by heating iodide [[(trifluoromethyl) sulfonyl] oxy] formylarene or a derivative thereof in the presence of an iron ion. .
  • the homo-coupled product is formed by binding an arene derivative at the 1,1'-position.
  • the homo-coupled product may have axial asymmetry due to the presence of substituents in the 2, 2 'position or in a mutually opposing positional relationship.
  • a homo-coupled product having such axial asymmetry is expected to be used as an asymmetry discriminating agent as it is by optical resolution.
  • the homo-coupled product can be further derivatized and multimerized, such as derivatization of the above-mentioned ditriflate formylbinaphthyl to ditriflate binaphthyl derivatives, substitution of trifluoromethylsulfonyl groups or iodine with other groups.
  • it is expected to be used as an asymmetric discrimination agent with improved asymmetric discrimination ability.
  • the NMR measurement results of the obtained (S) -4,4′-bis [[(trifluoromethyl) sulfonyl] oxy] -2,2′-diformyl-1,1′-binaphthyl are shown below.
  • the 1 H NMR spectrum is shown in FIGS. 1 and 2
  • the 13 C NMR spectrum is shown in FIGS. 3 and 4
  • the NOE correlation NMR spectrum related to hydrogen at the 3 and 3 ′ positions is shown in FIG. 5, and formyl.
  • the spectrum of NOE correlation NMR relating to the hydrogen of the radical is shown in FIG.
  • N, N′-diiodo-5,5-dimethylhydantoin (DIH, 17.0 g, 44.7 mmol) was added to a dichloromethane solution (40 mL) of 2-naphthaldehyde (2.00 g, 12.8 mmol).
  • Trifluoromethanesulfonic acid (TfOH, 7.93 mL, 89.6 mmol) was added dropwise.
  • the resulting solution was refluxed for 30 minutes, and then the reaction was terminated by adding an aqueous sodium sulfite solution. After separation and washing with water and brine, the dichloromethane layer was dried over magnesium sulfate and concentrated under reduced pressure. The obtained solid was washed with acetonitrile and filtered to obtain a white solid in a yield of 25%.
  • the obtained product was measured by NMR. Moreover, the obtained product was dissolved in a small amount of dichloromethane, recrystallized by adding hexane, and X-ray crystal structure analysis was performed. The bonding positions of iodine and trifluoromethylsulfonyloxy groups, which cannot be determined only by chemical shifts and coupling patterns of 13 C NMR and 1 H NMR, were clarified by X-ray crystal structure analysis. From these measurement results, the type of each substituent and the bonding position thereof were determined, and the product was identified as 3-trifluoromethylsulfonyloxy-5,7,8-triiodo-2-naphthaldehyde. The NMR measurement results of the product are shown below.
  • the diaryl derivative produced by the present invention and the binaphthyl derivative in the present invention are expected to introduce various substituents while maintaining the asymmetric structure.
  • the high-performance asymmetric in asymmetric synthesis and optical resolution is expected.
  • the formylarene derivative produced by the present invention is expected to introduce various substituents, and further expected as a raw material for a binaphthyl derivative having axial asymmetry by homocoupling. It is expected to be used as a high-performance asymmetric discrimination agent in optical resolution. Therefore, the present invention greatly contributes to the development of useful asymmetric synthesis catalysts and separation agents for optical isomers, and the development of new materials in various fields such as pharmaceuticals, chemical products, cosmetics, and electronic materials using them. Is expected to do.

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Abstract

La présente invention concerne un dérivé de diaryle ayant une structure asymétrique ou un procédé capable de produire un formylarène ayant deux groupes spécifiques de substituants, un nouveau dérivé de binaphtyle et un dérivé de formylarène. En utilisant un dérivé de diformyle-diaryle ayant une asymétrie axiale ou un formylarène comme produit de départ, l'acide trifluorométhanesulfonique est mis en réaction avec la N,N'-diiodo-5,5-diméthylhydantoïne dans des conditions douces et un dérivé de formyldiaryle comprenant des groupes trifluorométhylsulfoxy introduits en positions 4 et 4' ou un dérivé de formylarène comprenant un groupe trifluorométhylsulfoxy et de l'iode introduit est obtenu par le biais d'un procédé de réaction simple.
PCT/JP2011/055578 2010-03-11 2011-03-10 Procédé de production d'un dérivé de diaryle, nouveau dérivé de binaphtyle, procédé de production d'un dérivé d'arène et nouveau dérivé d'arène Ceased WO2011111762A1 (fr)

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WO2017145716A1 (fr) * 2016-02-22 2017-08-31 国立大学法人京都大学 Procédé de production de dérivé 1,1'-binaphtyle, et de dérivé 1,1'-binaphtyle
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CN112079754B (zh) * 2020-09-23 2021-10-26 四川大学 一种含活性基团含氟界面改性剂及其制备方法和应用

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