WO2005051878A1 - Zeolite porteuse d'aldehyde - Google Patents

Zeolite porteuse d'aldehyde Download PDF

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Publication number
WO2005051878A1
WO2005051878A1 PCT/JP2004/017551 JP2004017551W WO2005051878A1 WO 2005051878 A1 WO2005051878 A1 WO 2005051878A1 JP 2004017551 W JP2004017551 W JP 2004017551W WO 2005051878 A1 WO2005051878 A1 WO 2005051878A1
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Prior art keywords
zeolite
aldehyde
carbon atoms
substituent
functional group
Prior art date
Application number
PCT/JP2004/017551
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English (en)
Japanese (ja)
Inventor
Atushi Onaka
Takahiro Okaji
Original Assignee
Toudai Tlo Ltd
Atushi Onaka
Takahiro Okaji
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Application filed by Toudai Tlo Ltd, Atushi Onaka, Takahiro Okaji filed Critical Toudai Tlo Ltd
Priority to JP2005515805A priority Critical patent/JPWO2005051878A1/ja
Publication of WO2005051878A1 publication Critical patent/WO2005051878A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C47/00—Compounds having —CHO groups
    • C07C47/02—Saturated compounds having —CHO groups bound to acyclic carbon atoms or to hydrogen
    • C07C47/04—Formaldehyde
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
    • C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
    • C07C29/40—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing carbon-to-metal bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D207/06—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with radicals, containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated

Definitions

  • the present invention relates to a zeolite that supports or adsorbs an aldehyde, that is, an aldehyde-supporting zeolite, and a method for producing the zeolite.
  • the present invention also relates to a hydroxyalkylation method or 13-formylalkylation method using the aldehyde-supported zeolite.
  • formaldehyde is a versatile C1 electrophile.
  • formaldehyde is an unstable substance that is difficult to handle. That is, formaldehyde is extremely unstable in a gaseous state, and is disproportionated to methanol and formic acid in a state where it undergoes self-polymerization to form solid paraformaldehyde or in the presence of moisture. Therefore, formaldehyde was generally supplied before its use by depolymerizing paraformaldehyde or by heat treatment or Lewis acid treatment of trioxane.
  • Non-Patent Document 1 J. Am. Chem. Soc. 112, 7422 (1990).
  • Non-Patent Document 2 J. Am. Chem. Soc. 115, 3943 (1993).
  • an object of the present invention is to formaldehyde under room temperature conditions and in a monomer state. It is to provide a method that can be stored.
  • Another object of the present invention is to provide a method for effectively utilizing the versatile action of formaldehyde as a C1 electrophile.
  • Another object of the present invention is to provide a method for subjecting a nucleophile to hydroxyalkylation or / 3-formylalkylation using a zeolite supporting an aldehyde. Means for solving the problem
  • the amount of aldehyde molecules carried or adsorbed on zeolite is preferably 13 mmol, for example, 2 to 3 mmol per lg of zeolite.
  • the zeolite preferably has at least one kind selected from proton (H +), alkali metal, alkaline earth metal, and transition metal.
  • ⁇ 5> In the above ⁇ 3> or ⁇ 4>, at least one of them is preferably sodium.
  • the amount of aldehyde molecules carried or adsorbed by the zeolite is at least one kind of 1Z3 to 2Z3, preferably 1Z3 to 3Z5, more preferably 2Z5 to 3Z5. Is good.
  • the aldehyde may be a compound represented by the general formula RCHO (where R is H, a carbon atom which may have a substituent or a functional group, A linear or branched alkenyl group having 2 to 10 carbon atoms which may have a substituent or a functional group which may have a substituent or a functional group; — It may have a linear or branched alkynyl group of 10 or a substituent or a functional group! (Indicating an aromatic group having 412 to 20 carbon atoms).
  • RCHO where R is H, a carbon atom which may have a substituent or a functional group, A linear or branched alkenyl group having 2 to 10 carbon atoms which may have a substituent or a functional group which may have a substituent or a functional group; — It may have a linear or branched alkynyl group of 10 or a substituent or a functional group! (Indicating an aromatic group having 412 to 20 carbon atoms).
  • An alkaline having a step of placing a dehydrated zeolite in an atmosphere containing an aldehyde to obtain an aldehyde-supported zeolite in which the zeolite supports or adsorbs an aldehyde.
  • the amount of the aldehyde molecule carried or adsorbed on the zeolite is preferably 13 mmol per lg of zeolite, for example, 2 to 3 mmol.
  • the zeolite preferably has at least one selected from proton (H +), alkali metal, alkaline earth metal, and transition metal.
  • At least one of them is preferably an alkali metal.
  • At least one kind is preferably sodium.
  • R is H, a straight-chain or branched-chain alkyl group having 1-10 carbon atoms which may have a substituent or a functional group, a carbon atom having 2 or more carbon atoms which may have a substituent or a functional group, It may have a linear or branched alkenyl group having 2 to 10 carbon atoms, which may have a linear or branched alkenyl group, a substituent or a functional group, or a substituent or a functional group having 2 to 10 carbon atoms! (Indicating an aromatic group having 4 to 20 carbon atoms)).
  • R-CHO (wherein, R is H, a linear or branched alkyl group having 11 to 10 carbon atoms which may have a substituent or a functional group, a substituent or a functional group.
  • a method for hydroxyalkylation of a nucleophile comprising the step of:
  • R′—CH CH—CHO (wherein R ′ is H, straight-chain or branched-chain alkyl having 11 to 10 carbon atoms which may have a substituent or a functional group)
  • a nucleophile selected from the group consisting of 50 aromatic compounds, a carbanion having 1 to 20 carbon atoms, and an enol ether having 2 to 20 carbon atoms; )-A method for j8-formyl alkylation of a nucleophile, comprising a step of CH CHO.
  • the reaction is preferably carried out in a liquid phase, a gas phase or a solid phase.
  • the amount of the aldehyde molecule carried or adsorbed by the zeolite is preferably 13 mmol, for example, 2 to 3 mmol per lg of the zeolite.
  • the zeolite preferably has at least one selected from proton (H +), an alkali metal, an alkaline earth metal, and a transition metal.
  • At least one of them is preferably an alkali metal.
  • At least one is sodium.
  • the nucleophile is HSAB (Hard and a soft nucleophile (alkene, aromatic heterocyclic compound or enol ether) based on the theory of Soft Acid and Base.
  • the present invention can provide a method for hydroxyalkylating or 13-formylalkylating a nucleophile using a zeolite supporting an aldehyde.
  • the present invention provides an aldehyde-loaded zeolite having an aldehyde and a zeolite, wherein the zeolite supports or adsorbs the aldehyde.
  • the aldehyde-supported zeolite of the present invention can stably support an aldehyde at room temperature without causing self-polymerization of the aldehyde. Further, the aldehyde-supported zeolite of the present invention can be used as an electrophile by directly reacting with various nucleophiles in a state where the supported aldehyde remains as it is.
  • the aldehyde-carrying zeolite of the present invention can easily desorb aldehyde from zeolite by heating.
  • the aldehyde-supported zeolite of the present invention preferably has at least one selected from protons (H +), alkali metals, alkaline earth metals, and transition metals. It is preferred that the at least one is an alkali metal, more preferably sodium.
  • the zeolite is preferably of X type, Y type or j8 type. Preferably, it is Na-X type, Na-Y type, Na- ⁇ type, or ⁇ ⁇ - ⁇ type! / ⁇ .
  • the amount of aldehyde molecules supported or adsorbed on the zeolite is preferably 13 mmol, for example, 2-3 mmol per lg of zeolite.
  • the aldehyde-supported zeolite of the present invention has Na, it can support or adsorb aldehyde molecules depending on the content of Na, particularly the amount of Na occupying the zeolite surface area. That is, in the aldehyde-supported zeolite of the present invention, the amount of aldehyde molecules to be supported or adsorbed is 1Z3-2Z3, preferably 1Z3-3 / 5, more preferably 2 / 5—should be 3/5.
  • the aldehyde-supported zeolite of the present invention can adsorb or support the following aldehyde. That is, the aldehyde is a molecule represented by the general formula RCHO, wherein R is H, a linear or branched alkyl group having 1-10 carbon atoms which may have a substituent or a functional group.
  • R is H
  • a linear or branched alkenyl group having 2-10 carbon atoms which may have a substituent or a functional group It represents an alkynyl group or a C 420 aromatic group which may have a substituent or a functional group.
  • the substituent or the functional group include halogen, ketone, nitrile, ester, and ether.
  • the aldehyde-supported zeolite of the present invention can be prepared as follows. That is, it can be prepared by having a step of placing a sufficiently dehydrated zeolite in an atmosphere containing aldehyde.
  • zeolite and aldehyde are as described above.
  • the aldehyde-supported zeolite of the present invention exists in a pure state in which the adsorbed aldehyde does not undergo self-polymerization, and thus can be used for various methods using aldehyde.
  • the aldehyde-loaded zeolite of the present invention can be used in a method for hydroxyalkylating or j8-formylalkylating a nucleophile. That is, the present invention provides a method for hydroxyalkylating or j8-formylalkylating a nucleophile using an aldehyde-supported zeolite.
  • the hydroxyalkylation method of the nucleophile of the present invention is carried out according to the general formula R-CHO (where R is H, a straight-chain having 11 to 10 carbon atoms which may have a substituent or a functional group). Or a linear or branched alkenyl group having 2 to 10 carbon atoms which may have a substituted or unsubstituted alkyl group, a substituent or a functional group, or 2 to 10 carbon atoms which may have a substituted or functional group. Represents a linear or branched alkynyl group, or a C 420 aromatic group which may have a substituent or a functional group).
  • a zeolite that adsorbs aldehyde molecules, a linear or branched alkene having 2 to 50 carbon atoms which may have a substituent or a functional group, and a C 2 to 50 carbon atom which may have a substituent or a functional group; It may have a linear or branched alkyne, a substituent or a functional group, and may have a 3-20 membered cycloalkene or heterocyclized ring constituting a ring having a double bond.
  • the zeolite that supports or adsorbs an aldehyde used in the present invention is the aldehyde-supporting zeolite described above.
  • the “zeolite supporting or adsorbing aldehyde”, that is, the “aldehyde supporting zeolite” is referred to as the “step of converting a nucleophile into CH (R) OH” or “the nucleophile is CH (R ′)- Even if they are prepared before the “CH CHO process”,
  • the nucleophile used in the present invention is preferably a soft nucleophile based on the HSAB theory. For example, the following can be mentioned.
  • a linear or branched alkene having 2 to 50 carbon atoms which may have a substituent or a functional group or a linear or branched alkene having 2 to 50 carbon atoms which may have a substituent or a functional group.
  • An aromatic compound having the number of 4-50, a carbanion having the number of 120-120 carbons, and a group power including an enol ether having a number of carbons of 2-20 are also selected.
  • the nucleophile is an alkene, an aromatic heterocyclic compound, or an enol ether.
  • substituent or the functional group include halogen, ketone, nitrile, ester, and ether.
  • the nucleophile is a gas even if the nucleophile is used in a liquid phase in which a nucleophile is a solid, liquid or gas using a certain solvent. It may be performed in the gas phase or in a solid phase which is a solid.
  • zeolite is preferably a force depending on the nucleophile used.
  • the nucleophile when it is an alkene, it has a weak acid property.
  • a zeolite having the compound high yield and high selectivity can be obtained.
  • the nucleophile is ⁇ -methylstyrene, it is preferably a NaY zeolite.
  • Example 2 ⁇ Preparation of 3-Phenyl-3-buten-1-ol Using Formaldehyde-Supported Zeolite> ⁇ -Methylstyrene (118 mg) was dissolved in cyclohexane (4 ml). Formaldehyde-supported NaY (2 g, HCHO content: 2.4 mmol / g) prepared in the same manner was added. After stirring at room temperature for 1 hour, methanol (5 ml) was added, and NaY was removed by filtration. The NaY was further washed three times with methanol, the solvent was distilled off under reduced pressure, and the residue was purified using a silica gel column chromatography as usual. The distillate was distilled off under reduced pressure to obtain the desired compound (139 mg) as a colorless oil (yield 94%).
  • Limonene (136 mg) was dissolved in a mixed solvent of cyclohexane (3.6 ml) and hexane (0.4 ml), cooled to ⁇ 20 ° C., and the formaldehyde-bearing NaY was prepared in the same manner as in Example 1. (2 g, HCHO content: 2.4 mmol Zg) was added. — After stirring at 20 ° C for 1 hour, methanol (5 ml) was added, and then NaY was removed by filtration. The NaY was washed three more times with methanol, the solvent was distilled off under reduced pressure, and the residue was purified using silica gel column chromatography as usual. The distillate was distilled off under reduced pressure to obtain the target compound (153 mg) as a mixture of three kinds (yield 92%).
  • A1C1 (dimethylaluminum (III) salted product) was used at a reaction temperature of 25 ° C. to carry out a carbo-Louen reaction of limonene in the same manner as in Example 5. The result is described in “(HCHO), Me A1C1” of entry No. 9 in Table 1 described later.
  • Example 5 Instead of the formaldehyde-supported NaY (2 g, HCHO content: 2.4 mmol Zg) of Example 5, a bulky organoaluminum complex (trioxane, MAPH (methyl aluminum ( ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ) bis (2,6-diphenyl- Rifenoxide)) and the reaction temperature was 25 ° C., and the limonene carbonyl-reaction was carried out in the same manner as in Example 5. The results are shown in Table 1 below, entry No. 9 “trioxane , MAPH ”.
  • Examples 8 to 11 correspond to entry Nos. 5 to 8 in Table 1 below, and using the nucleophile (Substrate) and the reaction temperature (Reaction Temp) shown in the table, the yield (Isolated yield) shown in the table was used. ).
  • a sufficiently dehydrated NaY-type zeolite lg is placed in a flask, cooled to 0 ° C., and brought into contact with dry nitrogen gas containing acrolein (101 mg, 1.8 mmol) vapor, so that about 1.8 mmol of acrolein per lg of zeolite is adsorbed or absorbed.
  • a supported acrolein-supported zeolite was obtained. Faku It was confirmed that lorrain was retained in the zeolite without being polymerized.
  • a similar product was obtained by directly heating a mixture of dried zeolite (NaY, lg), acrolein (lOlmg), and asol (20 mL) at 145 ° C. This indicates that the step of carrying and / or adsorbing acrolein on zeolite and the step of reacting acrolein and azole of the zeolite carrying the acrolein are performed in concert. ing. This also indicates that the desired product can be obtained by reacting zeolite with acrolein and anol as a nucleophile without preparing the zeolite carrying acrolein in advance. You.
  • Example 14 also shows that a desired product can be obtained by reacting zeolite, acrolein and sol as a nucleophile in the same manner as in Example 13.
  • Example 15 also shows that a product can be obtained by reacting zeolite, acrolein and indole as a nucleophile in the same manner as in Example 13.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyrrole Compounds (AREA)
  • Indole Compounds (AREA)

Abstract

Cette invention se rapporte à un procédé permettant de conserver du formaldéhyde sous forme monomère à température ambiante, et à un procédé servant à hydroxyalkyler un réactif nucléophile au moyen d'une zéolite porteuse d'aldéhydes. Ces procédés sont réalisés par une zéolite porteuse d'aldéhydes comprenant un aldéhyde et une zéolite, laquelle porte ou adsorbe l'aldéhyde. Cette invention concerne en outre un procédé servant à hydroxyalkyler un réactif nucléophile, qui consiste à mettre en réaction une zéolite portant ou adsorbant une molécule d'aldéhyde de formule générale R-CHO avec un agent nucléophile choisi dans le groupe constitué par un alcène, un alcyne, un composé cyclique insaturé éventuellement substitué, un composé aromatique éventuellement substitué, un carbanion, des éthers d'énol, un réactif de Grignard et un composé organométallique, afin de convertir l'agent nucléophile en -CH(R)-OH.
PCT/JP2004/017551 2003-11-27 2004-11-26 Zeolite porteuse d'aldehyde WO2005051878A1 (fr)

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JP2005515805A JPWO2005051878A1 (ja) 2003-11-27 2004-11-26 アルデヒド担持ゼオライト

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5289570A (en) * 1976-01-22 1977-07-27 Asahi Chem Ind Co Ltd Gaseous phase separation
JPS53149909A (en) * 1977-05-31 1978-12-27 Asahi Chem Ind Co Ltd Separation and purification of formaldehyde
JPS55113732A (en) * 1979-01-05 1980-09-02 Mobil Oil Manufacture of alcohol product
JPS56113725A (en) * 1980-02-14 1981-09-07 Mitsubishi Chem Ind Ltd Separation of aliphatic aldehyde isomer mixture
JPH04500071A (ja) * 1988-07-13 1992-01-09 インラッド，インコーポレーテッド 直鎖アルカン炭化水素の末端塩素化

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5289570A (en) * 1976-01-22 1977-07-27 Asahi Chem Ind Co Ltd Gaseous phase separation
JPS53149909A (en) * 1977-05-31 1978-12-27 Asahi Chem Ind Co Ltd Separation and purification of formaldehyde
JPS55113732A (en) * 1979-01-05 1980-09-02 Mobil Oil Manufacture of alcohol product
JPS56113725A (en) * 1980-02-14 1981-09-07 Mitsubishi Chem Ind Ltd Separation of aliphatic aldehyde isomer mixture
JPH04500071A (ja) * 1988-07-13 1992-01-09 インラッド，インコーポレーテッド 直鎖アルカン炭化水素の末端塩素化

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