Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B61/00—Other general methods

Definitions

• the present invention relates to silyl acetals, oligosiloxanes, and methods for producing them, and more particularly, to methods for producing silyl acetals using iridium complexes and the like, methods for producing oligosiloxanes using Lewis acids, and methods for producing these
• the present invention relates to silyl acetals and oligosiloxanes that can be produced in the same manner.
• Siloxane bonds (Si-O-Si) have higher bond energy than carbon-carbon bonds (CC) and carbon-oxygen bonds (CO), which are organic skeletons. It is known that the compound is excellent in durability, weather resistance and the like.
• the formation method of siloxane bond has been actively studied for a long time. Typical methods include hydrolysis / dehydration condensation of silanol, alkoxysilane, chlorosilane, etc., cross-coupling of chlorosilane and silanol (or alkoxysilane). A method by cross coupling of hydrosilane and silanol (or alkoxysilane) is known.
• An object of the present invention is to provide a useful intermediate that can be efficiently derived into oligosiloxane or oligosiloxane.
• the present inventors have found that acyloxysilane and hydrosilane react in the presence of an iridium complex to produce silylacetal, and further, the produced silylacetal is a Lewis acid.
• the inventors found that an oligosiloxane is produced by causing intramolecular rearrangement in the presence of the present invention, thereby completing the present invention. That is, the present invention is as follows.
• R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms
• R 2 each independently represents a hydrocarbon having 1 to 18 carbon atoms.
• R 3 each independently has a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having a hydrocarbon group having 1 to 12 carbon atoms, or a hydrocarbon group having 3 to 18 carbon atoms.
• ⁇ 3> including a rearrangement step of reacting a silyl acetal having a structure represented by the following formula (C) in the presence of a Lewis acid to produce an oligosiloxane having a structure represented by the following formula (D).
• a method for producing an oligosiloxane In the formulas (C) to (D), R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.
• ⁇ 4> The method for producing an oligosiloxane according to ⁇ 3>, wherein the Lewis acid is a boron compound having Lewis acidity.
• the silyl acetal having the structure represented by the formula (C) is an acyloxysilane having the structure represented by the following formula (A) and the following formula (B) in the presence of an iridium complex and / or an iridium salt.
• R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.
• R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.
• R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.
• R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.
• R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms
• R 2 represents Each independently a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having a hydrocarbon group having 1 to 12 carbon atoms, a silyloxy group having a hydrocarbon group having 3 to 18 carbon atoms
• R 3 and R 4 are each independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, or a hydrocarbon group having 1 to 12 carbon atoms.
• a useful silyl acetal that can be efficiently derived into oligosiloxane and oligosiloxane can be provided.
• the method for producing a silyl acetal which is one embodiment of the present invention includes an acyloxysilane having a structure represented by the following formula (A) and a structure represented by the following formula (B) in the presence of an iridium complex and / or an iridium salt.
• addition step for producing a silyl acetal having a structure represented by the following formula (C) by reacting hydrosilane having: (In the formulas (A) to (C), R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.)
• R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.
• silyl acetal which has a structure represented by Formula (C) obtained by an addition process is a useful compound which can be efficiently induced
• the wavy lines in the formulas (A) to (C) mean that the structure ahead is arbitrary.
• the “addition process” will be described in detail.
• an acyloxysilane having a structure represented by the formula (A) and a hydrosilane having a structure represented by the formula (B) are reacted with each other in the formula (C).
• an acyloxysilane having a structure represented by the formula (A) and a hydrosilane having a structure represented by the formula (B) are reacted with each other in the formula (C).
• the specific kind of acylsilane which has a structure represented by Formula (A), and the hydrosilane which has a structure represented by Formula (B) is especially limited Rather, it should be appropriately selected according to the target oligosiloxane.
• acyloxysilane having a structure represented by the formula (A) examples include acyloxysilane represented by the following formula (A-1).
• R 1 is a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms
• R 2 is independently a hydrocarbon group having 1 to 18 carbon atoms
• R 1 represents a “hydrogen atom” or “hydrocarbon group having 1 to 18 carbon atoms”, and the “hydrocarbon group” includes a branched structure, a cyclic structure, and a carbon-carbon unsaturated bond (carbon- Each of which may have a carbon double bond, carbon-carbon triple bond), and may be any of a saturated hydrocarbon group, an unsaturated hydro
• an oxygen atom such as an ether group (—O—), an oxygen atom such as a silyloxy group (—O—Si—), a silicon atom, or a functional group (linking group) containing a halogen atom is present inside or at the end of the carbon skeleton. May be included.
• a hydrocarbon group having 2 carbon atoms including an ether group such as —CH 2 —O—CH 3 (methoxymethyl group) and a silyloxy group such as —CH 2 —O—Si (CH 3 ) 3 are included.
• a hydrocarbon group having 4 carbon atoms (trimethylsilyloxymethyl group) and the like are included.
• the number of carbon atoms when R 1 is a hydrocarbon group is preferably 12 or less, more preferably 6 or less, and the number of carbon atoms when R 1 is an aromatic hydrocarbon group is usually 6 or more. .
• R 1 includes a hydrogen atom, a methyl group (—CH 3 , —Me), an ethyl group (—C 2 H 5 , —Et), an n-propyl group ( —n C 3 H 7 , —n Pr), i -Propyl group ( -i C 3 H 7 , -i Pr), n-butyl group ( -n C 4 H 9 , -n Bu), t-butyl group ( -t C 4 H 9 , -t Bu), n-pentyl group ( -n C 5 H 11 ), n-hexyl group ( -n C 6 H 13 , -n Hex), cyclohexyl group ( -c C 6 H 11 , -Cy), phenyl group (-C 6 H 5 , —Ph), a naphthyl group (—C 12 H 7 , —Naph), and the like.
• a methyl group
• R 2 each independently has a “hydrocarbon group having 1 to 18 carbon atoms”, an “alkoxy group having a hydrocarbon group having 1 to 12 carbon atoms”, or a “hydrocarbon group having 3 to 18 carbon atoms”.
• the term “silyloxy group”, “acyloxy group having a hydrocarbon group having 1 to 18 carbon atoms”, or “halogen atom” is the same as the case of R 1 .
• the number of carbon atoms when R 2 is a hydrocarbon group is preferably 12 or less, more preferably 6 or less, and the number of carbon atoms when R 2 is an aromatic hydrocarbon group is usually 6 or more. .
• the number of carbon atoms when R 2 is an alkoxy group is preferably 10 or less, more preferably 6 or less.
• the number of carbon atoms when R 2 is a silyloxy group is preferably 10 or less, more preferably 6 or less.
• the number of carbon atoms when R 2 is an acyloxy group is preferably 12 or less, more preferably 6 or less.
• R 2 includes a methyl group (—CH 3 , —Me), an ethyl group (—C 2 H 5 , —Et), an n-propyl group ( —n C 3 H 7 , —n Pr), and an i-propyl group.
• Examples of the acyloxysilane represented by the formula (A-1) include those represented by the following formula.
• Examples of the hydrosilane having a structure represented by the formula (B) include a hydrosilane represented by the following formula (B-1).
• each R 3 independently represents a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having a hydrocarbon group having 1 to 12 carbon atoms, or 3 to 3 carbon atoms. Represents a silyloxy group having 18 hydrocarbon groups or a halogen atom.
• R 3 each independently has a “hydrocarbon group having 1 to 18 carbon atoms”, “an alkoxy group having a hydrocarbon group having 1 to 12 carbon atoms”, or “a hydrocarbon group having 3 to 18 carbon atoms”.
• the term “silyloxy group” or “halogen atom” is used, but the “hydrocarbon group” has the same meaning as in R 1 .
• the number of carbon atoms when R 3 is a hydrocarbon group is preferably 12 or less, more preferably 6 or less, and the number of carbon atoms when R 3 is an aromatic hydrocarbon group is usually 6 or more.
• R 3 is an alkoxy group the number of carbon atoms is preferably 10 or less, more preferably 6 or less.
• R 3 is a silyloxy group the number of carbon atoms is preferably 10 or less, more preferably 6 or less.
• R 3 includes a hydrogen atom, a methyl group (—CH 3 , —Me), an ethyl group (—C 2 H 5 , —Et), an n-propyl group ( —n C 3 H 7 , —n Pr), i -Propyl group ( -i C 3 H 7 , -i Pr), n-butyl group ( -n C 4 H 9 , -n Bu), t-butyl group ( -t C 4 H 9 , -t Bu), n-pentyl group ( -n C 5 H 11 ), n-hexyl group ( -n C 6 H 13 , -n Hex), cyclohexyl group ( -c C 6 H 11 , -Cy), phenyl group (-C 6 H 5 , -Ph), naphthyl group (-C 12 H 7 , -Naph), methoxy group (-OCH 3 , -OM
• hydrosilane represented by the formula (B-1) examples include those represented by the following formula.
• the use amount (charge amount) of the hydrosilane having the structure represented by the formula (B) is usually 0.3 times or more, preferably in terms of the amount of substance, in terms of the amount of the acyloxysilane having the structure represented by the formula (A). Is 0.5 times or more, more preferably 1 time or more, and usually 5 times or less, preferably 3 times or less, more preferably 1.5 times or less. Within the above range, silyl acetal can be more efficiently produced.
• the addition step is a step performed in the presence of an iridium complex and / or an iridium salt (hereinafter sometimes abbreviated as “iridium complex etc.”), but the iridium oxidation number, ligand or The specific type of counter ion is not particularly limited, and can be appropriately selected according to the purpose.
• the oxidation number of iridium is usually 0, +1, +2, +3, +4, +5, and +6, but is preferably +1.
• Examples of the ligand or counter ion, or a compound capable of becoming such include cyclooctene, 1,5-cyclooctadiene, ethylene, norbornadiene, chloride anion (Cl ⁇ ), bromide anion (Br ⁇ ) and the like.
• Examples of the iridium complex include chlorobis (cyclooctene) iridium (I) dimer ([Ir (coe) 2 Cl] 2 ), chloro (1,5-cyclooctadiene) iridium (I) dimer ([Ir (cod) Cl ] 2 ) etc. are mentioned.
• a silyl acetal can be more efficiently produced as described above.
• the amount of iridium complex or the like used is usually 0.0001 times or more, preferably 0.001 times or more, more preferably, in terms of the amount of the substance with respect to the acyloxysilane having the structure represented by the formula (A). Is 0.005 times or more, usually 0.5 times or less, preferably 0.1 times or less, more preferably 0.05 times or less. Within the above range, silyl acetal can be more efficiently produced.
• a solvent is preferably used.
• the type of the solvent is not particularly limited and can be appropriately selected according to the purpose.
• the solvent is a hydrocarbon solvent such as hexane, benzene, or toluene; an ether type such as diethyl ether or tetrahydrofuran (THF).
• Solvent Halogen-based solvents such as methylene chloride and chloroform. Of these, benzene is particularly preferred. A silyl acetal can be more efficiently produced as described above.
• the reaction temperature in the addition step is usually ⁇ 80 ° C. or higher, preferably 0 ° C. or higher, more preferably 20 ° C. or higher, and usually 120 ° C. or lower, preferably 80 ° C. or lower, more preferably 40 ° C. or lower.
• the reaction time in the addition step is usually 1 hour or longer, preferably 6 hours or longer, more preferably 12 hours or longer, and usually 96 hours or shorter, preferably 48 hours or shorter, more preferably 24 hours or shorter.
• the addition step can be performed in the air, but is preferably performed in an inert atmosphere such as nitrogen or argon. Within the above range, silyl acetal can be more efficiently produced.
• R 3 each independently has a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having a hydrocarbon group having 1 to 12 carbon atoms, or a hydrocarbon group having 3 to 18 carbon atoms. Represents a silyloxy group or a halogen atom.
• Examples of the silyl acetal represented by any one of the formulas (C-1) to (C-4) include those represented by the following formula.
• a method for producing an oligosiloxane which is another embodiment of the present invention (hereinafter sometimes abbreviated as “method for producing an oligosiloxane of the present invention”) is represented by the following formula (C) in the presence of a Lewis acid. It includes a rearrangement step (hereinafter sometimes abbreviated as “rearrangement step”) in which an oligosiloxane having a structure represented by the following formula (D) is produced by reacting a silyl acetal having the following structure: .
• R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.
• the present inventors have found that acyloxysilane and hydrosilane react with each other in the presence of an iridium complex to produce silyl acetal, and the generated silyl acetal undergoes intramolecular rearrangement in the presence of a Lewis acid, resulting in oligosiloxane. Was found to generate efficiently. Since the above-described addition step and rearrangement step proceed rapidly under relatively mild conditions, the method for producing oligosiloxane by combining the addition step and rearrangement step is basically a by-product at the stage where the oligosiloxane is formed.
• the wavy line in the formulas (C) to (D) means that the structure ahead is arbitrary.
• the “dislocation process” will be described in detail.
• the rearrangement step is a step of reacting a silyl acetal having a structure represented by the formula (C) in the presence of a Lewis acid to produce an oligosiloxane having a structure represented by the formula (D).
• the specific kind of the silyl acetal having the structure represented by C) is not particularly limited, and can be appropriately selected according to the target oligosiloxane.
• Examples of the silyl acetal having a structure represented by the formula (C) include silyl acetals represented by any one of the above-described formulas (C-1) to (C-4).
• it is preferable that the silyl acetal which has a structure represented by Formula (C) is what was obtained by the above-mentioned addition process.
• the oligosiloxane production method combining the addition step and the rearrangement step can produce oligosiloxane more efficiently and also suppress by-products.
• the rearrangement step is a step performed in the presence of a Lewis acid.
• the Lewis acid is not particularly limited as long as it is a compound having Lewis acidity, and can be appropriately selected according to the purpose.
• the Lewis acid tris (pentafluorophenyl) borane (B (C 6 F 5 ) 3 ) is preferable.
• An oligosiloxane can be produced more efficiently when it is as described above.
• the use amount (charge amount) of the Lewis acid is usually 0.0001 times or more, preferably 0.001 times or more, more preferably, in terms of the amount of the silyl acetal having the structure represented by the formula (C). It is 0.005 times or more, usually 0.5 times or less, preferably 0.1 times or less, more preferably 0.05 times or less. When it is within the above range, oligosiloxane can be produced more efficiently.
• the rearrangement step preferably uses a solvent.
• the type of the solvent is not particularly limited and can be appropriately selected according to the purpose.
• the solvent is a hydrocarbon solvent such as hexane, benzene, or toluene; an ether type such as diethyl ether or tetrahydrofuran (THF).
• Solvent Halogen-based solvents such as methylene chloride and chloroform. Of these, benzene is particularly preferred. An oligosiloxane can be produced more efficiently when it is as described above.
• the reaction temperature in the rearrangement step is usually ⁇ 80 ° C. or higher, preferably 0 ° C. or higher, more preferably 20 ° C. or higher, and usually 120 ° C. or lower, preferably 80 ° C. or lower, more preferably 40 ° C. or lower.
• the reaction time in the rearrangement step is usually 1 minute or more, preferably 5 minutes or more, more preferably 10 minutes or more, and usually 96 hours or less, preferably 48 hours or less, more preferably 24 hours or less.
• the rearrangement step can be performed in the air, but is preferably performed in an inert atmosphere such as nitrogen or argon. When it is within the above range, oligosiloxane can be produced more efficiently.
• the silyl acetal represented by the formula (C) is preferably obtained by the above-described addition step.
• the silyl acetal having the structure represented by the formula (C) is:
• the addition step and rearrangement step proceed in one reactor. There may be.
• oligosiloxane can be produced sequentially in one pot, and the oligosiloxane can be produced very efficiently.
• the oligosiloxane production method of the present invention is not particularly limited as long as it includes the above-described rearrangement step, but is represented by the following formula (D) obtained in the rearrangement step in the presence of a Lewis acid.
• a substitution step (hereinafter referred to as “substitution step”) in which an oligosiloxane having a structure and a hydrosilane having a structure represented by the following formula (E) are reacted to produce an oligosiloxane having a structure represented by the following formula (F) May be omitted).
• substitution step in which an oligosiloxane having a structure and a hydrosilane having a structure represented by the following formula (E) are reacted to produce an oligosiloxane having a structure represented by the following formula (F) May be omitted).
• R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.
• the wavy lines in the formulas (D) to (F) mean that the structure ahead is arbitrary.
• the oligosiloxane having the structure represented by the formula (D) obtained in the rearrangement step is reacted with the hydrosilane having the structure represented by the formula (E) to form a structure represented by the formula (F).
• Specific types of oligosiloxane having a structure represented by the formula (D) and hydrosilane having a structure represented by the formula (E) are not particularly limited. It should be appropriately selected depending on the oligosiloxane to be used. Examples of the oligosiloxane having a structure represented by the formula (D) include those represented by any of the following formulas (D-1) to (D-4).
• R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms
• R 2 each independently represents a hydrocarbon having 1 to 18 carbon atoms.
• R 3 each independently has a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having a hydrocarbon group having 1 to 12 carbon atoms, or a hydrocarbon group having 3 to 18 carbon atoms. Represents a silyloxy group or a halogen atom.
• “R 1 ”, “R 2 ”, and “R 3 ” are the same as those described above.
• Examples of the hydrosilane having a structure represented by the formula (E) include a hydrosilane represented by the following formula (E-1).
• each R 4 independently represents a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having a hydrocarbon group having 1 to 12 carbon atoms, or 3 to 3 carbon atoms. Represents a silyloxy group having 18 hydrocarbon groups or a halogen atom.
• R 4 each independently has a “hydrocarbon group having 1 to 18 carbon atoms”, an “alkoxy group having a hydrocarbon group having 1 to 12 carbon atoms”, or a “hydrocarbon group having 3 to 18 carbon atoms”.
• the term “silyloxy group” or “halogen atom” is used, but the “hydrocarbon group” has the same meaning as in R 1 .
• the number of carbon atoms when R 4 is a hydrocarbon group is preferably 12 or less, more preferably 6 or less, and the number of carbon atoms when R 4 is an aromatic hydrocarbon group is usually 6 or more.
• R 4 is an alkoxy group, the number of carbon atoms is preferably 10 or less, more preferably 6 or less.
• R 4 is a silyloxy group the number of carbon atoms is preferably 10 or less, more preferably 6 or less.
• R 4 includes a hydrogen atom, a methyl group (—CH 3 , —Me), an ethyl group (—C 2 H 5 , —Et), an n-propyl group ( —n C 3 H 7 , —n Pr), i -Propyl group ( -i C 3 H 7 , -i Pr), n-butyl group ( -n C 4 H 9 , -n Bu), t-butyl group ( -t C 4 H 9 , -t Bu), n-pentyl group ( -n C 5 H 11 ), n-hexyl group ( -n C 6 H 13 , -n Hex), cyclohexyl group ( -c C 6 H 11 , -Cy), phenyl group (-C 6 H 5 , -Ph), naphthyl group (-C 12 H 7 , -Naph), methoxy group (-OCH 3 , -OM
• hydrosilane represented by the formula (E-1) examples include those represented by the following formula.
• the amount of use of the hydrosilane having the structure represented by the formula (E) (charge amount) is usually 0.5 times or more, preferably in terms of the amount of the substance based on the oligosiloxane having the structure represented by the formula (D). Is 0.8 times or more, more preferably 1.0 times or more, usually 5 times or less, preferably 2 times or less, more preferably 1.5 times or less. When it is within the above range, oligosiloxane can be produced more efficiently.
• the substitution step is a step performed in the presence of a Lewis acid
• the Lewis acid is not particularly limited as long as it is a compound having Lewis acidity, and can be appropriately selected according to the purpose.
• the Lewis acid tris (pentafluorophenyl) borane (B (C 6 F 5 ) 3 ) is preferable.
• An oligosiloxane can be produced more efficiently when it is as described above.
• the use amount (charge amount) of the Lewis acid is usually 0.0001 times or more, preferably 0.001 times or more, more preferably, in terms of the amount of substance with respect to the oligosiloxane having the structure represented by the formula (D). It is 0.005 times or more, usually 0.5 times or less, preferably 0.1 times or less, more preferably 0.05 times or less. When it is within the above range, oligosiloxane can be produced more efficiently.
• the solvent is a hydrocarbon solvent such as hexane, benzene, or toluene; an ether type such as diethyl ether or tetrahydrofuran (THF).
• Solvent Halogen-based solvents such as methylene chloride and chloroform. Of these, benzene is particularly preferred. An oligosiloxane can be produced more efficiently when it is as described above.
• the reaction temperature in the substitution step is usually ⁇ 80 ° C. or higher, preferably 0 ° C. or higher, more preferably 20 ° C. or higher, and usually 120 ° C. or lower, preferably 80 ° C. or lower, more preferably 40 ° C. or lower.
• the reaction time of the substitution step is usually 1 minute or more, preferably 5 minutes or more, more preferably 10 minutes or more, and usually 96 hours or less, preferably 48 hours or less, more preferably 24 hours or less.
• the replacement step can be performed in the air, but is preferably performed in an inert atmosphere such as nitrogen or argon. When it is within the above range, oligosiloxane can be produced more efficiently.
• the substitution step is a step of reacting the oligosiloxane having the structure represented by the formula (D) obtained in the rearrangement step.
• the oligosiloxane having the structure represented by the formula (D) is isolated and purified.
• hydrosilane having a structure represented by the formula (E) may be introduced into the reactor after the rearrangement step, and the substitution step may proceed as it is.
• oligosiloxane can be produced sequentially in one pot, and the oligosiloxane can be produced very efficiently.
• oligosiloxane is generated by the rearrangement step and the substitution step, but the following formulas (D-1) to (D-4) and the following formulas (F-1) to (F) that can be generated by the rearrangement step or the like. -2) is also an embodiment of the present invention.
• R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms
• R 2 represents Each independently a hydrocarbon group having 1 to 18 carbon atoms, an alkoxy group having a hydrocarbon group having 1 to 12 carbon atoms, a silyloxy group having a hydrocarbon group having 3 to 18 carbon atoms
• R 3 and R 4 are each independently a hydrogen atom, a hydrocarbon group having 1 to 18 carbon atoms, or a hydrocarbon group having 1 to 12 carbon atoms.
• Examples of the oligosiloxane represented by any of the following formulas (D-1) to (D-4) and the following formulas (F-1) to (F-2) include those represented by the following formula.
• Example 1 Me 3 SiOAc (90.2 ⁇ L, 0.60 mmol) and mesitylene (internal standard, 21.0 ⁇ L, 0.15 mmol) were dissolved in deuterated benzene C 6 D 6 (3.0 mL). This solution (0.5 mL) was added to an NMR tube containing [Ir (coe) 2 Cl] 2 (0.5 mg, 1 mol% Ir), followed by Et 2 SiH 2 (14.2 ⁇ L, 0.11 mmol). It was. After 12 hours, it was confirmed by 1 H NMR measurement that silylacetal was produced in a yield of 88%.
• Example 2 The reaction was performed in the same manner as in Example 1 except that Et 2 SiH 2 was changed to MePhSiH 2 (15.1 ⁇ L, 0.11 mmol). As a result, the yield of silyl acetal was 79%, the yield of disiloxane was 65%, and the yield of trisiloxane was 63%.
• Trisiloxane (colorless oil) 1 H NMR (C 6 D 6 ): 7.71-7.68 (m, 6H), 7.19-7.15 (m, 9H), 5.90 (s, 1H), 0.39 (s 3H), 0.09 (s, 9H) ppm.
• Example 7 The reaction was performed in the same manner as in Example 1 except that Ph 2 SiH 2 was changed to MePhSiH 2 (15.1 ⁇ L, 0.11 mmol). As a result, the yield of silyl acetal was 79%, the yield of disiloxane was 79%, and the yield of trisiloxane was 70%.
• Example 9 The reaction was performed in the same manner as in Example 1 except that Ph 2 SiH 2 was changed to Et 3 SiOSiH 2 Ph (25.9 ⁇ L, 0.10 mmol). As a result, the yield of silyl acetal was 93%, the yield of disiloxane was 83%, and the yield of tetrasiloxane was 74%. Tetrasiloxane (colorless oil) 1 H NMR (C 6 D 6 ): 7.79-7.77 (m, 2H), 7.25-7.18 (m, 3H), 5.44 (s, 1H), 1.06-1 .00 (m, 15H), 0.65-0.60 (m, 10H), 0.15 (s, 9H) ppm.
• Example 10 The reaction was performed in the same manner as in Example 1 except that Ph 2 SiH 2 was changed to PhSiH 3 (6.1 ⁇ L, 0.05 mmol). As a result, the yield of silyl acetal was 85%, the yield of disiloxane was 71%, and the yield of oligosiloxane was 52%.
• Example 11 Et 2 SiH 2 and MePhSiH 2 (15.1 ⁇ L, 0.11mmol) was changed to, except that the Ph 2 SiH 2 MePhSiH 2 (13.7 ⁇ L , 0.10mmol) , the reaction in the same manner as in Example 1 Went. As a result, the yield of silyl acetal was 96%, and the yield of trisiloxane was 71%.
• Trisiloxane (colorless oil, diastereo ratio 1: 1)
• Oligosiloxane produced by the production method of the present invention can be used as a raw material for silicone oil, silicone rubber, organic-inorganic hybrid material and the like.

Landscapes

• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (1)

Family

ID=59790575

Family Applications (1)

Country Status (2)

Cited By (3)

Families Citing this family (1)

Family Cites Families (10)

• 2017
  • 2017-03-06 JP JP2018504480A patent/JP6703287B2/ja active Active
  • 2017-03-06 WO PCT/JP2017/008836 patent/WO2017154848A1/ja not_active Ceased
• 2019
  • 2019-10-28 JP JP2019195624A patent/JP6938048B2/ja active Active

Non-Patent Citations (4)

Also Published As

Similar Documents

Legal Events