JP4377635B2 - Organotin compound and method for producing the same - Google Patents

Description

  The present invention relates to a method for producing an organotin compound (such as stannyl alkene) from alkynyltin and a hydrogen molecule using a novel organotin compound and a transition metal catalyst, and a catalyst (or catalyst system) useful for this method.

  Organotin compounds have been proposed for use in the field of organic synthesis as key intermediates for many pharmaceuticals and functional substances. Furthermore, the organotin compound has an advantage that it is more stable to water and air than an organometallic compound containing an alkali metal or alkaline earth metal used for a similar reaction in an organic synthetic method. From such a background, development of a safe and economical method for producing organotin compounds is expected.

  For example, Organometallics, 1994, 13, 947 (Non-patent Document 1) reports a method for producing alkenyl tin by coupling an organomagnesium compound formed from an alkenyl halide and a tin halide. Also, Synlett, 1999, 246 (Non-patent Document 2) and Chemistry Letters, 1989, 981 (Non-patent Document 3) use a transition metal catalyst such as palladium, and alkenyl tin by reaction of alkyne with tin hydride reagent. Manufacturing methods have been reported.

  However, in the method of Non-Patent Document 1, it is necessary to use an organic halogen compound that has a high environmental load. Moreover, in the manufacturing method of nonpatent literature 2-3, the isomer ratio of the alkenyl tin obtained is not necessarily high. Therefore, it is difficult to obtain an alkenyl tin compound with high stereoselectivity.

JP-A-2002-275186 (Patent Document 1) reacts an unsaturated hydrocarbon (olefinic or acetylenically unsaturated compound) with an alkynyltin compound in the presence of a catalyst composed of a transition metal element. Discloses a method for producing an organotin compound having an unsaturated bond. Although this method can produce an organotin compound having a conjugated enyne site or a conjugated diene site, it cannot produce a simple alkenyltin compound.
Organometallics, 1994, 13, 947 Synlett, 1999, 246 Chemistry Letters, 1989, 981 JP 2002-275186 A (Claims)

  Accordingly, an object of the present invention is to provide a novel alkenyl tin compound.

  Another object of the present invention is to provide a method capable of easily and efficiently producing stannylalkenes and a catalyst (or catalyst system) useful for this method.

  Still another object of the present invention is to provide a method capable of producing an alkenyl tin compound with high stereoselectivity, and a catalyst (or catalyst system) useful for this method.

  Another object of the present invention is to provide a method for easily and efficiently producing a deuterated alkenyl tin compound (or deuterated olefins), and a catalyst (or catalyst system) useful for this method.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have reacted hydrogen molecules with an alkynyltin compound in the presence of a transition metal catalyst. The present inventors have found that an organic tin compound (2-stannyl-1-alkene) containing a compound can be obtained in a high yield, and that an organic tin compound can be efficiently produced with high regioselectivity, thereby completing the present invention.

  That is, the novel organotin compound of the present invention is represented by the following formula (1a).

(Wherein, X ¹ and X ² are the same or different and each represents a hydrogen atom or deuterium atom, when X ¹ and X ² are hydrogen atom, R ¹ represents an alkyl group or an aryl group, R ² is An alkyl group having a substituent selected from a carboxyl group, an alkoxycarbonyl group, an amide group, and an N-substituted amide group; an alkoxy group; a substituted aryl group; a heterocyclic group; or a group R ¹ ₃ Sn—C≡C— ( R ¹ represents the same as above.) When X ¹ and X ² are deuterium atoms, R ¹ and R ² are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, aralkyl group, an alkoxy group, a heterocyclic group, or the formula _{^{R 1 3 Sn-C≡C- (R}} 1 is as defined above) a group represented by the alkyl group, an alkenyl group, an aryl group, an aralkyl group, Alkoxy and heterocyclic groups are substituted May have a group)
In the formula (1a), R ¹ usually represents an alkyl group, and R ² usually has a substituent selected from a carboxyl group, an alkoxycarbonyl group, an amide group, and an N-substituted amide group. An alkyl group; an alkoxy group; a substituted aryl group; a heterocyclic group; or a group R ¹ ₃ Sn—C≡C— (R ¹ is the same as above), and X ¹ and X ² are usually the same or different and represent hydrogen An atom or a deuterium atom.

  In the present invention, an organic tin compound is produced by reacting a hydrogen molecule or deuterium molecule with an alkynyltin compound in the presence of a catalyst composed of a transition metal element. The transition metal element is usually at least one element selected from Group 4 elements of the periodic table to Group 11 elements of the periodic table (for example, at least one element selected from Group 6 elements of the periodic table and Group 8 elements of the periodic table). Transition metal element). The catalyst may constitute a catalyst system. For example, the catalyst system is combined with a compound (a promoter or a reaction accelerator) containing at least one element selected from the Group 15 element of the periodic table and the Group 16 element of the periodic table (for example, a compound containing the Group 15 element of the periodic table). It may be configured. That is, the reaction may be performed in the presence of the promoter.

  The reaction may be performed by reacting a hydrogen molecule or deuterium molecule with an alkynyltin compound in the presence of the catalyst or catalyst system, and the product is a hydrogenated or deuterated organic compound corresponding to the alkynyltin compound. Tin compounds such as stannyl alkenes can be mentioned. That is, a deuterated organotin compound can be produced by reacting a deuterium molecule with an alkynyltin compound.

  The present invention also includes a catalyst or catalyst system for producing an organotin compound by reacting a hydrogen molecule or deuterium molecule with an alkynyltin compound. This catalyst or catalyst system can be composed of at least a transition metal element. The catalyst or catalyst system may further contain a compound containing at least one element selected from Group 15 elements of the periodic table and Group 16 elements of the periodic table. For example, the catalyst for producing a stannyl alkene by reacting a hydrogen molecule or deuterium molecule with an alkynyl tin compound is at least one selected from Group 6 elements of the periodic table and Group 8 elements of the periodic table You may comprise with the compound containing a transition metal element and the compound containing a periodic table 15 group element.

  In the present specification, molecules containing deuterium (deuterium) D and / or tritium (tritium) T may be collectively referred to as “deuterium molecules”. Further, “hydrogen molecule and deuterium molecule” may be simply referred to as “hydrogen molecule”.

  In the present invention, a novel organotin compound having a terminal alkenyl group (such as a vinyl group) can be provided. In addition, since hydrogen molecules or deuterium molecules are reacted with alkynyltin compounds in the presence of a catalyst, organotin compounds (such as stannylalkenes) can be produced easily and efficiently. In particular, stannylalkenes can be produced with high regioselectivity. Furthermore, a deuterated alkenyl tin compound (or deuterated olefin) can be produced simply and efficiently simply by using deuterium.

  In the present invention, a hydrogen molecule or deuterium molecule is reacted with an alkynyltin compound in the presence of a specific catalyst to produce a corresponding organotin compound (or hydrogenated organotin compound).

[Catalyst or catalyst system]
The catalyst is composed of a transition metal element, and the transition metal element includes a group 3 element to a group 11 element in the periodic table. Examples of such transition metal elements include Group 3 elements of the periodic table (such as Sc, Y and rare earth elements), Group 4 elements of the periodic table, Group 5 elements of the periodic table, Group 6 elements of the periodic table, and Group 7 elements of the periodic table. Group elements, Group 8 elements of the periodic table, Group 9 elements of the periodic table, Group 10 elements of the periodic table (Ni, Pd, Pt, etc.), Group 11 elements of the periodic table (Cu, Ag, Au, etc.), etc. . These transition metal elements can be used at least one (single or in combination of two or more).

  Preferred transition metal elements include, for example, Group 4 elements of the periodic table (Ti, Zr, Hf, etc.), Group 5 elements of the periodic table (V, Nb, Ta, etc.), Group 6 elements of the periodic table (Cr, Mo, etc.). W etc.), Periodic Table Group 7 elements (Mn, Tc, Re etc.), Periodic Table Group 8 elements (Fe, Ru, Os etc.), Periodic Table Group 9 elements (Co, Rh, Ir etc.), Platinum At least one selected from Further preferred transition metals include Group 6 elements of the periodic table (chromium, molybdenum, tungsten), Group 8 elements of the periodic table (ruthenium), and Group 9 elements of the periodic table (rhodium, iridium). In particular, at least one transition metal element selected from Group 6 elements of the periodic table (chromium, tungsten) and Group 8 elements of the periodic table (ruthenium), such as ruthenium, is included. The oxidation number of the element is not particularly limited, and may be 0, +2, +3, +4, for example, depending on the type of element.

  The transition metal source may be a single metal, but is usually used as a compound of a transition metal element. Transition metal element compounds include, for example, inorganic acid salts (eg, nitrates, sulfates, perhalogenates, hydrohalides such as hydrochloric acid, hydrobromic acid, etc.), organic acid salts (eg, methane) Sulfonic acid salts such as sulfonic acid, ethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, phosphonates, formic acid, acetic acid, propionic acid, and the like, and halides (for example, Chloride, bromide, iodide, etc.), metal oxides (chromium oxide, tungsten oxide, ruthenium oxide, etc.), complexes (or complex salts), and the like. The transition metal catalyst may be a solid catalyst in which the metal or metal compound is fixed to a support such as activated carbon, silica, alumina, titania or the like.

Examples of the ligand constituting the complex include OH (hydroxo), C _1-4 alkoxy group, C _1-4 acyl group, C _1-4 alkoxy-carbonyl group, acetylacetonato, cyclopentadienyl group, Cyclooctadienyl group, benzylidene group, vinylidene group, benzylideneacetone, benzylideneacetylacetonate, benzylideneacetophenone, cycloalkadiene such as cyclooctadiene, aromatic compounds such as benzene, toluene, cymene, cumene, xylene, naphthalene, halogen Atoms, CO, CN, oxygen atoms, H ₂ O (aquo), phosphines (eg, triarylphosphines such as triphenylphosphine), phosphites (eg, triarylphosphites such as triphenylphosphite), NH ₃ ( ammine), NO, NO ₂ (nits ), NO ₃ (nitrato), ethylenediamine, diethylenetriamine, pyridine, phenanthroline, bipyridyl, acetonitrile, benzonitrile, and other nitrogen-containing compounds such as tert- octyl isocyanide. In the complex or complex salt, one or two or more of the same or different ligands may be coordinated. Further, for example, a plurality of the transition metal atoms may be contained in one molecule complex or complex salt such as a cluster compound such as dodecacarbonyl triruthenium.

Typical complexes or complex salts include, for example, carbonyl (dihydrido) tris (triphenylphosphine) ruthenium [RuH ₂ (CO) (PPh ₃ ) ₃ ], dicarbonyltris (triphenylphosphine) ruthenium [Ru (CO) ₂ (PPh ₃ ) ₃ ], dodecacarbonyl triruthenium [Ru ₃ (CO) ₁₂ ], dichlorotris (triphenylphosphine) ruthenium [RuCl ₂ (PPh ₃ ) ₃ ], dichloro (1,5-cyclooctadiene) ruthenium Ru (cod) Cl ₂ , trichlororuthenium [RuCl ₃ ], ruthenium (acetylacetonate) [Ru (acac) ₃ ], ruthenocene, tetrachlorobis (η-p-cymene) diruthenium [RuCl ₂ (η-p-cymene) )] ₂ , bis (tricyclohexylphosphine) benzylidene ruthenium chloride, (1,5-cyclooctadiene) (1,3,5-cyclooctatriene) ruthenium Of the ruthenium complexes or complex salts such as Ru (cod) (cot), di (dimethyl fumarate) (1,5-cyclooctadiene) ruthenium Ru (cod) (dmfu) ₂ , and the corresponding transition metal sources In many cases, compounds of transition metal elements, particularly complexes or complex salts are used. Further, the complex or complex salt may be generated in the reaction system. For example, tetrachlorobis (η-benzene) diruthenium may be added to the tetrachlorobis (η-benzene) diruthenium by a method in which p-cymene is added separately. [eta] -p-cymene) diruthenium may be produced.

[Cocatalyst (or Ligand)]
The catalyst of the present invention may constitute a catalyst system in combination with a promoter (or ligand). When the reaction is carried out in the presence of such a cocatalyst (or a ligand or a reaction accelerator), the reactivity and selectivity can be improved.

As the ligand (or co-catalyst), among the above-mentioned “ligands constituting the complex”, usually from Group 15 elements (nitrogen, phosphorus, etc.) and Group 16 elements (oxygen, sulfur, etc.) of the periodic table. It can be composed of a compound containing at least one selected element. For example, CN, phosphine (for example, triarylphosphine such as triphenylphosphine, trialkylphosphine such as tributylphosphine, tricycloalkylphosphine such as tricyclohexylphosphine), bisphosphine (1,3-bis (diphenylphosphino) propane Bis (arylphosphino) alkanes, etc.), phosphites (eg triaryl phosphites such as triphenyl phosphite), nitrogen-containing compounds [NH ₃ (ammine), NO, NO ₂ (nitro), NO ₃ ( Nitrato), ethylenediamine, diethylenetriamine, pyridine, phenanthroline, bipyridyl, acetonitrile, benzonitrile, tert-octyl isocyanide, and the like. The ligand is a ligand containing two or more elements of Group 15 to Group 16 of the periodic table in the molecule, such as aminophosphines [for example, dialkylamino group and diphenylphosphino group or dialkylphosphino group. Such as N, N-dimethyl-N-{[2- (diphenylphosphino) phenyl] methyl} amine, N, N-dimethyl-N- [2- (diphenylphosphino) phenyl] amine Etc.]. In the reaction system, one or two or more of the same or different ligands may be used.

  The ratio of the ligand is, for example, about 0.001 to 1000 mol, preferably about 0.1 to 100 mol, more preferably about 1 to 50 mol, and about 2 to 20 mol with respect to 1 mol of the transition metal catalyst. There are many cases.

[Method for producing organotin compound]
In the present invention, by reacting an alkynyltin compound represented by the following formula (2) with a hydrogen molecule or deuterium molecule represented by the following formula (3) in the presence of the catalyst or catalyst system, An organotin compound represented by the formula (1) can be produced. In this reaction, when a deuterium molecule is reacted with an alkynyltin compound, a deuterated organotin compound can be obtained.

[Wherein, R ^1a , R ^1b , R ^1c and R ^2a are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, a heterocyclic group, an alkoxy group or the following formula ( Group represented by 4)

(R ^1a , R ^1b and R ^1c are the same as above), and the alkyl group, alkenyl group, aryl group, aralkyl group, heterocyclic group or alkoxy group may have a substituent, and X ¹ and X ² is the same or different and represents a hydrogen atom or a deuterium atom]
[Alkynyl tin compounds]
In the alkynyl tin compound (2), the halogen atom includes fluorine, chlorine, bromine and iodine atoms. Examples of the alkyl group include linear or branched C _1-20 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, octyl, decyl, and dodecyl groups. (Preferably a C _1-10 alkyl group, particularly a C _1-6 alkyl group) can be exemplified. The alkenyl group includes linear or branched C _2-20 alkenyl groups (preferably C _2-10 alkenyl groups, particularly C _2-6 alkenyl groups) such as vinyl, propenyl, isopropenyl, allyl and butenyl groups. It can be illustrated.

Aryl groups include C _6-14 aryl groups such as phenyl and naphthyl groups, and aralkyl groups include C _6-10 aryl-C _1-4 alkyl groups such as benzyl and phenethyl groups.

  The heterocyclic group includes a 5- or 6-membered heterocyclic group containing at least one heteroatom selected from nitrogen, oxygen and sulfur atoms as a constituent atom of the ring, and a condensed heterocyclic group obtained by condensing a heterocyclic ring and a hydrocarbon ring. And the heterocyclic group may be an aromatic or non-aromatic heterocyclic group. Examples of the heterocyclic compound corresponding to such a heterocyclic group include sulfur-containing heterocyclic compounds such as thiophene, oxygen-containing heterocyclic compounds such as furan, chromene, and chromane, pyrrole, imidazole, pyridine, indole, quinoline, and carbazole. And nitrogen-containing heterocyclic compounds such as acridine, phenazine, piperidine, piperazine and morpholine.

Examples of the alkoxy group include linear or branched C _1-10 alkoxy groups (preferably C _1-6 alkoxy groups) such as methoxy, ethoxy, propoxy, butoxy and t-butoxy.

The substituent can be selected according to the kind of the alkyl group, alkenyl group, aryl group, aralkyl group, heterocyclic group or alkoxy group. Substituents include halogen atoms (fluorine, chlorine, bromine, iodine atoms), linear or branched alkyl groups (C _1-6 alkyl groups such as methyl, ethyl, butyl, t-butyl groups, especially C _{1 -4} alkyl groups), linear or branched haloalkyl groups (such as halo C _1-4 alkyl groups such as trichloromethyl, trifluoromethyl, tetrafluoropropyl groups), linear or branched alkenyl groups (vinyl) C _2-6 alkenyl groups such as propenyl, isopropenyl and butenyl groups, preferably C _2-4 alkenyl groups, aryl groups (C _6-14 aryl groups such as phenyl groups), aralkyl groups (benzyl, phenethyl groups, etc.) C _6-10 aryl -C _1-4 alkyl group), a hydroxyl group, a linear or branched alkoxy group (methoxy, ethoxy, butoxy, C _1-6 a, such as t- butoxy Kokishi group), C _1-6 alkylthio groups corresponding to the alkoxy group, an aryloxy group (phenoxy group), a carbonyl group (or keto group), an acyl group (formyl group, acetyl, C, such as propionyl group _1-6 Alkyl-carbonyl group, aromatic acyl group such as benzoyl group), carboxyl group, linear or branched alkoxy-carbonyl group (C _1-6 alkoxy-carbonyl group such as methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl group, etc.) ), Aryloxycarbonyl groups (such as phenoxycarbonyl groups), amino groups, N-substituted amino groups (N-mono C _1-4 alkylamino groups such as methylamino and butylamino groups, dimethylamino, diethylamino, and dibutylamino groups) of N, N-di-C _1-4 alkylamino group, a, such as an acetylamino group Etc. arylamino group), an amide group, N- substituted amide group (N-C _1-4 alkyl amide group, N, N- di-C _1-4 alkyl amide group, etc.), a nitro group, a cyano group can be exemplified. The substituents of the groups R ^1a , R ^1b , R ^1c and R ^2a are usually different from the groups R ^1a , R ^1b , R ^1c and R ^2a , for example, R ^1a , R ^1b , When R ^1c and R ^2a have a hydrocarbon group such as an alkyl group or an aryl group, a halogen atom, haloalkyl group, hydroxyl group, carboxyl group, alkoxy group, alkoxycarbonyl group, cyano group or the like may be substituted.

  The alkynyltin compound (2) is not particularly limited as long as it is a compound containing at least one ethynyltin moiety in the molecule (or an alkenyltin compound containing an ethynyltin bond, etc.), and various compounds such as a trialkylalkynyltin compound , Dialkyl dialkynyl tin compounds, monoalkyl trialkynyl tin compounds, tetraalkynyl tin compounds and the like can be used, and these compounds may have a substituent.

Examples of trialkylalkynyltin include tri-C _1- , such as trimethyl (ethynyl) tin, tributyl (ethynyl) tin, trimethyl (propynyl) tin, tributyl (propynyl) tin, trimethyl (octynyl) tin, tributyl (octynyl) tin, and the like. ₁₀ alkyl C _2-16 alkynyl tin, preferably tri C _1-4 alkyl (C _2-10 alkynyl) tin; tri C _1-10 alkyl (C ₆ ) such as trimethyl (phenylethynyl) tin, tributyl (phenylethynyl) tin _-10 aryl-C _2-16 alkynyl) tin, preferably tri-C _1-4 alkyl (phenyl-C _2-10 alkynyl) tin; tri-C _1-10 alkyl (C ₅ ) such as tributyl (3-thienylethynyl) tin hetero cycle -C _2-16 alkynyl) tin to _-6, preferably hetero cycle to tri C _1-4 alkyl (C _5-6 Such as C _2-10 alkynyl) tin can be exemplified.

Examples of the dialkyl dialkynyl tin include diC _1-10 alkyldi (C _2-16 alkynyl) tin such as dibutyldi (ethynyl) tin, dibutyldi (propynyl) tin, dibutyldi (octynyl) tin, preferably diC _1-6 Alkyl di (C _2-10 alkynyl) tin; diC _1-10 alkyldi (C _6-14 aryl-C _2-16 alkynyl) tin, such as dibutyldi (phenylethynyl) tin, preferably diC _1-6 alkyldi (phenyl- C _2-10 alkynyl) tin and the like.

Examples of the monoalkyltrialkynyltin include C _1-10 alkyltri (C _2-16 alkynyl) tin such as butyltri (ethynyl) tin, butyltri (propynyl) tin, butyltri (octynyl) tin, preferably C _1-6 Alkyltri (C _2-10 alkynyl) tin; butyltri (phenylethynyl) tin C _1-10 alkyltri (C _6-14 aryl-C _2-16 alkynyl) tin, preferably C _1-6 alkyltri (phenyl-C Examples include _2-10 alkynyl) tin.

Examples of tetraalkynyl tin include tetra C _2-16 alkynyl tin such as tetraethynyl tin, tetrapropynyl tin, and tetraoctynyl tin, preferably tetra C _2-10 alkynyl tin; tetra (C _6-14 such as tetraphenylethynyl tin). Aryl-C _2-16 alkynyl) tin, preferably tetra (phenyl-C _2-10 alkynyl) tin is exemplified.

As a typical alkynyltin having a substituent, a compound having a halogen atom [triC _1-10 alkyl (halophenylethynyl) tin such as tributyl (4-chlorophenylethynyl) tin, tributyl (4-bromophenylethynyl) tin, etc. Etc.], a compound having an alkyl group [triC _1-10 alkyl (C _1-4 alkylphenylethynyl) tin such as tributyl (4-methylphenylethynyl) tin], a compound having a haloalkyl group [tributyl (4-triphenyl) Tri-C _1-10 alkyl (haloC _1-4 alkylphenylethynyl) tin such as fluoromethylphenylethynyl) tin], a compound having a hydroxyl group [6-tributylstannyl-5-hexyn-1-ol and the like C _1-10 alkyl (hydroxy C _2-16 alkynyl) tin, tributyl 4-methoxyphenyl-ethynyl) tri C _1-10 alkyl (C _1-4 alkoxyphenyl ethynyl such as tin) tin, etc.], tri C _1-10 alkyl such as a compound having an alkoxy group [2-tributylstannyl ethynyl ether (C _1-4 alkoxy C _2-16 alkynyl) tin], a compound having a carboxyl group or an alkoxycarbonyl group [7-tributylstannyl-6-heptynoic acid methyl ester and the like tri-C _1-10 alkyl (carboxy or C _{1 -4} alkoxy-carbonyl C _2-16 alkynyl) tin], compounds having an amide group [N, N-dimethyl-7-tributylstannyl-6-heptanoic acid amide and the like tri-C _1-10 alkyl (carbamoyl C _{2- 16} alkynyl) tin or its N-alkyl-substituted amide], compounds having a nitrile group [6-tributyls And tri-C _1-10 alkyl (cyano C _2-16 alkynyl) tin such as tanyl-5-hexinonitrile].

The alkynyltin compound includes a tin hydride having a hydrogen atom in the tin atom (for example, a di-C _1-10 alkyl (C _2-10 alkynyl) tin hydride such as dibutyl (ethynyl) tin hydride), and a halogen in the tin atom. Also included are chin halides having atoms (for example, di-C _1-10 alkyl (C _2-10 alkynyl) chin halides such as dibutyl (ethynyl) tin chloride). Furthermore, the alkynyl tin compound includes a compound in which the hydrogen atom of the alkynyl group of the acetylene compound is substituted with a tin atom. As the alkynyl tin compound, an alkynyl tin compound generated in the reaction system by hydrostannylation, distanylation reaction, reaction of tin halide and acetylene compound, or the like may be used.

[Hydrogen molecule]
Hydrogen molecules include hydrogen allotrope atoms (deuterium (deuterium) ² H: D, tritium (tritium) ³ ), in addition to hydrogen molecules (H—H) formed by normal hydrogen atoms ( ¹ H) having a mass number of 1. H: T), for example, HD, DD, HT, DT, TT. These hydrogen molecules can be used alone or in combination of two or more. A normal hydrogen molecule or deuterium molecule is used as the hydrogen molecule.

  Furthermore, the hydrogen molecule may be generated in the reaction system from a dehydrogenable compound (hydrocarbon such as cyclohexane, secondary or primary alcohol such as 2-propanol). Alternatively, hydrogen molecules may be generated in the system by reducing water or alcohol.

  Of the organotin compounds produced by the reaction, preferred compounds (3) are stannylalkenes. The organotin compound contains a new compound. That is, the novel organotin compound of the present invention is represented by the following formula (1a), an organotin compound having a normal hydrogen atom and a specific substituent, and an organotin having a deuterium atom (D or T). Compound.

(Wherein, X ¹ and X ² are the same or different and each represents a hydrogen atom or deuterium atom, when X ¹ and X ² are hydrogen atom, R ¹ represents an alkyl group or an aryl group, R ² is An alkyl group having a substituent selected from a carboxyl group, an alkoxycarbonyl group, an amide group, and an N-substituted amide group; an alkoxy group; a substituted aryl group; a heterocyclic group; or a group R ¹ ₃ Sn—C≡C— ( R ¹ represents the same as above.) When X ¹ and X ² are deuterium atoms, R ¹ and R ² are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, An aralkyl group, an alkoxy group, a heterocyclic group or a group represented by the formula (4), wherein the alkyl group, alkenyl group, aryl group, aralkyl group, alkoxy group and heterocyclic group have a substituent; Also good)
In the formula (1a), usually R ¹ represents an alkyl group or an aryl group, and R ² represents an alkyl group having a substituent selected from a carboxyl group, an alkoxycarbonyl group, an amide group, and an N-substituted amide group. An alkoxy group; a substituted aryl group; a heterocyclic group; or a group R ¹ ₃ Sn—C≡C— (wherein R ¹ is the same as above), and X ¹ and X ² are the same or different and represent a hydrogen atom or a deuterium atom; Indicates.

Examples of the substituent of the formula (1a) include the atoms and substituents corresponding to R ^1a , R ^1b , R ^1c and R ^2a exemplified in the paragraphs of the formulas (1) to (3). That is, R ^1a , R ^1b and R ^1c in the formulas (1) to (3) correspond to R ¹ in the formula (1a), and R ^{2a in the} formulas (1) to (3) represents the formula (1a). ) R ² .

In the formula (1a), the alkyl group represented by R ¹ is usually a linear or branched C _1-10 alkyl group (particularly a C _1-6 alkyl group). The aryl group represented by R ¹ is usually a C _6-10 aryl group (particularly a phenyl group). These alkyl groups and aryl groups may have the same substituent as the alkyl group and aryl group represented by R ^2a or R ² .

The alkyl group represented by R ² is usually a linear or branched C _1-20 alkyl group (preferably a C _1-10 alkyl group, particularly a C _1-6 alkyl group). The alkoxycarbonyl group as a substituent for R ² is usually a C _1-6 alkoxy-carbonyl group (particularly a C _1-4 alkoxy-carbonyl group). Amide group, a substituted group, for example, may have a methyl group, an ethyl group, a C _1-4 alkyl group or a C _1-4 alkylcarbonyl group such as butyl group, N- substituted amide group, a mono-substituted It may be an amide group (N-alkylamide group or the like) or a disubstituted amide group (N, N-dialkylamide group or the like). The number in particular of these substituents is not restrict | limited, Usually, about 1-4 may be sufficient. The substitution position of the substituent may be an alkyl group end, a side chain, or a branched chain.

The alkoxy group represented by R ² is usually a linear or branched C _1-6 alkoxy group (particularly a C _1-4 alkoxy group).

The substituted aryl group includes a halogen atom (fluorine, chlorine, bromine or iodine atom), a linear or branched C _1-6 alkyl group (particularly a C _1-4 alkyl group), a linear or branched halo. C _1-6 alkyl group (especially halo C _1-6 alkyl group such as chloromethyl, fluoromethyl, trichloromethyl, trifluoromethyl, perfluoropropyl group), hydroxyl group, linear or branched C _1-6 Alkoxy group (especially C _1-4 alkoxy group), carboxyl group, linear or branched C _1-6 alkoxy-carbonyl group (especially C _1-4 alkoxy-carbonyl group), amide group, N-substituted amide Examples thereof include a C _6-10 aryl group (particularly a phenyl group) having at least one substituent selected from a group and the like. The number of substituents for the aryl group may usually be about 1 to 4. The substitution position of the substituent is the o-, m-, p-position, 2,6-, 3,5-, 3,4,5-, 2,4,6-position of the aryl group (eg, phenyl group). It may be.

Examples of the heterocyclic group represented by R ² include the heterocyclic groups exemplified above, for example, a 5- or 6-membered heterocyclic group containing at least one heteroatom selected from nitrogen, oxygen and sulfur atoms as a constituent atom of the ring. (For example, thienyl group, furyl group, pyrrolyl group, imidazolyl group, pyridyl group, morpholino group, etc.), condensed heterocyclic groups in which these 5- or 6-membered heterocyclic groups are condensed with hydrocarbon rings (benzene rings, etc.), etc. Can be illustrated.

When at least one (one or both) of X ¹ and X ² is a deuterium atom, the alkyl group, alkenyl group, aryl group, aralkyl group, alkoxy group, heterocyclic group represented by R ¹ and R ² Examples thereof include the same groups as described above. As the substituent of these groups, the same substituents as described in the above-mentioned alkynyltin compound (halogen atom, alkyl group, haloalkyl group, hydroxyl group, alkoxy group, carboxyl group, alkoxycarbonyl group, amino group, N-substituted amino group, amide group, N-substituted amide group, cyano group, etc.).

In the formula (1a), R ¹ is usually an alkyl group, and R ² is usually an alkyl group, an alkoxy group, an aryl group, a heterocyclic group, or a group R ¹ ₃ Sn—C≡C— ( R ¹ is the same as above.

  Such a novel compound is also easily produced by reacting an alkynyltin compound corresponding to formula (1a) with a hydrogen molecule or deuterium molecule among the compounds represented by formula (2) in the presence of the catalyst. it can.

[Reaction solvent]
The reaction between the alkynyltin compound (2) and the hydrogen molecule or deuterium molecule (3) may be performed in the absence of a solvent or in the presence of a solvent. For example, the reaction may be carried out in a solution system using a solvent, a solventless system without using a solvent, a gas phase flow reaction system, or the like. A preferred reaction is an easy solution system such as control of the reaction temperature.

  The solvent is not particularly limited. For example, ethers (diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, dimethoxyethane, etc.), hydrocarbons (aliphatic hydrocarbons such as n-hexane, heptane, octane, etc.) Cyclohexane, cyclopentane, cyclohexene, cyclopentene and other alicyclic hydrocarbons, benzene, toluene, xylene and other aromatic hydrocarbons), halogenated hydrocarbons, dimethyl sulfoxide, sulfolane and other sulfur-containing solvents Is mentioned. In addition, components that are not liquid at normal temperature and pressure, such as carbon dioxide, ethane, and fluorocarbon in a supercritical state, can be used if they can be used in a fluid state.

  Further, the solvent may be a nitrogen-containing solvent. The nitrogen-containing solvent is not particularly limited as long as it is a compound having a nitrogen atom in the molecule. For example, ammonia solvents such as liquid ammonia and ammonia water, amine compounds such as triethylamine, diethylamine, diisopropylamine, ethylenediamine, pyrrolidine and piperidine, nitrogen-containing heterocyclic compounds such as pyridine, α-picoline, imidazole and pyrrole, N, Amide compounds such as N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidinone, urea compounds such as N, N-dimethylpropylene urea, phosphate amide compounds such as hexamethylphosphoramide, acetonitrile, benzo Nitrile compounds such as nitrile are included. The solvent can also be used as a mixed solvent.

  The amount of the solvent is, for example, 0 to 10,000 parts by weight, preferably 0 to 100 parts by weight, and more preferably 0 to 50 parts by weight with respect to 1 part by weight of the alkynyltin compound.

  The ratio of each component in the reaction can be selected within a range in which the catalytic activity is not impaired and the stability can be maintained depending on the type of each catalyst component. The ratio of the transition metal catalyst is, for example, about 0.000001 to 1 mol, preferably 0.0001 to 0.5 mol, and more preferably about 0.0005 to 0.2 mol with respect to 1 mol of the alkynyltin compound. In many cases, it is about 0.001 to 0.1 mole times. Moreover, the ratio of the ligand is as described above.

  The reaction temperature can be selected from a wide range of, for example, about −100 to 300 ° C. (for example, −50 to 200 ° C.), and is usually about 0 to 150 ° C. (for example, 30 to 120 ° C.). The reaction time can be arbitrarily selected in consideration of, for example, economy.

  Hydrogen molecules may be charged into the reaction vessel as hydrogen gas at an appropriate ratio (for example, a ratio of 1 mol or more with respect to alkynyltin), and are not particularly limited by conditions such as pressure and concentration of hydrogen molecules. Depending on the pressure and temperature conditions, the hydrogen molecule may be used in the form of liquefied hydrogen or in a critical state.

  The space inside the reaction vessel may be filled with a gas other than hydrogen, and the gas to be filled must be a flame-supporting gas such as oxygen within a concentration range that takes safety into consideration. There is no particular limitation other than. Examples of such gases include hydrocarbons such as methane, ethane, ethylene, and butadiene, nitrogen compounds such as ammonia, nitrogen dioxide, nitric oxide, and hydrogen cyanide, sulfur compounds such as hydrogen sulfide, carbon disulfide, and sulfur dioxide. Carbon monoxide and carbon dioxide may be used. A preferable reaction is carried out in a reaction system using only hydrogen or a reaction system using a rare gas such as argon or an inert gas such as nitrogen together with hydrogen. The pressure of the reaction system may be, for example, 0.0001 to 100 MPa, preferably 0.001 to 10 MPa, more preferably 0.01 to 1 MPa as the total pressure in the reactor at the reaction temperature.

  After completion of the reaction, the product may be isolated using a conventional separation and purification means such as concentration, drying, crystallization, recrystallization, filtration, extraction, distillation, chromatography and the like.

  INDUSTRIAL APPLICABILITY The present invention can obtain an alkenyl tin compound (olefin compound) from an alkynyl tin compound, and is useful for obtaining a reagent, a pharmaceutical or agricultural chemical intermediate, and a polymerizable compound. Deuterated compounds can also be used as labeling compounds.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1
In a 20 mL glass reaction vessel, dimethyl sulfoxide (DMSO) (0.3 mL), carbonyl (dihydrido) tris (triphenylphosphine) ruthenium (RuH ₂ (CO) (PPh ₃ ) ₃ , 5 mol%, 18.4 mg, 0.020 mmol) and tributylphosphine (30 mol%, 0.12 mmol) were added and stirred. Furthermore, tributyl (octynyl) tin (0.40 mmol) was added, and fully substituted with hydrogen gas (normal pressure). The mixture was stirred at 80 ° C. for 6 hours. The conversion rate of tributyl (octynyl) tin was determined by measuring the reaction end solution by gas chromatography and found to be 100%. The reaction solution was treated with water (5 mL) and extracted with ether (20 mL × 3 times). Thereafter, the organic layers were combined, washed with saturated brine (10 mL), and dried over anhydrous magnesium sulfate. After concentration, the residue was isolated by gel permeation chromatography GPC (chloroform), whereby 2-tributylstannyl-1-octene was obtained in a yield of 89% (mol%) based on alkynyl tin.

2-Tributylstannyl-1-octene: yellow oily substance
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.85-0.91 (m, 18H)
1.25-1.54 (m, 20H), 2.23 (t, J = 7.5 Hz, 2H), 5.08 (dt, J = 3.0, 1.2 Hz, 1H), 5. 67 (dt, J = 3.0, 1.5 Hz, 1H);
¹³ C-NMR (75 MHz, CDCl ₃ ) δ: 9.5, 13.6, 14.0, 22.
6, 27.3, 28.9, 29.1, 29.6, 31.7, 41.4, 124.6, 156.0;
¹¹⁹ Sn { ¹ H} -NMR (186 MHz, CDCl ₃ ) δ: -47.5;
Elemental analysis (C ₂₀ H ₄₂ Sn)
Calculated C 59.87; H 10.55
Found C 59.99; H 10.19.

Comparative Example 1
When the reaction was carried out in the same manner as in Example 1 except that the reaction time was 30 hours without adding carbonyl (dihydrido) tris (triphenylphosphine) ruthenium, no product was obtained.

Example 2
Example 1 except that dodecacarbonyltriruthenium (5 mol%, 4.3 mg, 6.7 μmol as Ru) was used in place of carbonyl (dihydrido) tris (triphenylphosphine) ruthenium and the reaction time was 30 hours. As a result of the reaction, 2-tributylstannyl-1-octene was obtained in a yield of 79% at a conversion rate of 100%. The yield is mol% based on alkynyl tin determined by gas chromatography measurement.

Example 3
The reaction was conducted in the same manner as in Example 1 except that 6-tributylstannyl-5-hexyn-1-ol was used instead of tributyl (octynyl) tin and the reaction time was 12 hours. 5-Tributylstannyl-5-hexen-1-ol was obtained in 89% yield.

5-Tributylstannyl-5-hexen-1-ol: yellow oily substance
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.85-0.91 (m, 13
H), 1.24-1.62 (m, 19H), 2.26 (t, J = 7.5 Hz, 2H), 3.65 (t, J = 6.2 Hz, 2H), 5.10 ( dt, J = 3.0, 0.9 Hz, 1H), 5.66 (dt, J = 3.0, 1.2 Hz, 1H);
¹³ C-NMR (75 MHz, CDCl ₃ ) δ: 9.4, 13.5, 25.5, 27.
3, 29.0, 32.3, 40.8, 62.7, 125.0, 155.3;
¹¹⁹ Sn { ¹ H} -NMR (186 MHz, CDCl ₃ ) δ: −47.2.

Example 4
The reaction was conducted in the same manner as in Example 1 except that 7-tributylstannyl-6-heptynoic acid methyl ester was used in place of tributyl (octynyl) tin and the reaction time was 30 hours. -6-Tributylstannyl-6-heptenoate was obtained with a yield of 65%.

Methyl-6-tributylstannyl-6-heptenoate: yellow oily substance
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.85-0.91 (m, 15H
), 1.24-1.67 (m, 16H), 2.25 (t, J = 7.5 Hz, 2H), 2.31 (t, J = 7.5 Hz, 2H), 3.66 (s) 3H), 5.10 (dt, J = 3.0, 1.2 Hz, 1H), 5.66 (dt, J = 3.0, 1.5 Hz, 1H);
¹³ C-NMR (75 MHz, CDCl ₃ ) δ: 9.4, 13.5, 24.5, 27.
3, 28.9, 29.0, 33.8, 40.7, 51.4, 125.1, 155.0, 174.3;
¹¹⁹ Sn { ¹ H} -NMR (186 MHz, CDCl ₃ ) δ: −47.0.

Example 5
When reacted in the same manner as in Example 1 except that N, N-dimethyl-7-tributylstannyl-6-heptanoic acid amide was used in place of tributyl (octynyl) tin, and the reaction time was 14 hours, The conversion was 100%, and N, N-dimethyl-6-tributylstannyl-6-heptanoic acid amide was obtained in a yield of 71%.

N, N-dimethyl-6-tributylstannyl-6-heptanoic acid amide: yellow oily substance
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.85-0.91 (m, 15H)
, 1.24-1.66 (m, 16H), 2.26 (t, J = 7.5 Hz, 2H), 2.31 (t, J = 7.5 Hz, 2H), 2.94 (s, 3H), 3.00 (s, 3H), 5.10 (dt, J = 2.7, 0.9 Hz, 1H), 5.66 (dt, J = 2.7, 1.5 Hz, 1H);
¹³ C-NMR (75 MHz, CDCl ₃ ) δ: 9.4, 13.6, 24.8, 27.
3, 29.0, 29.2, 33.2, 35.3, 37.2, 40.9, 125.0, 155.3, 173.2;
¹¹⁹ Sn { ¹ H} -NMR (186 MHz, CDCl ₃ ) δ: −47.2.

Example 6
The reaction was conducted in the same manner as in Example 1 except that 6-tributylstannyl-5-hexenonitrile was used instead of tributyl (octynyl) tin and the reaction time was 48 hours. Tributylstannyl-5-hexenonitrile was obtained with a yield of 70%.

5-Tributylstannyl-5-hexenonitrile: yellow oily substance
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.85-0.92 (m, 15H)
, 1.31 (sex, J = 7.2 Hz, 6H), 1.43-1.53 (m, 6H), 1.74 (quint, J = 7.2 Hz, 2H), 2.31 (t, J = 7.2 Hz, 2H), 2.38 (t, J = 7.2 Hz, 2H), 5.20 (q, J = 1.2 Hz, 1H), 5.66 (q, J = 1.2 Hz) , 1H);
¹³ C-NMR (75 MHz, CDCl ₃ ) δ: 9.4, 13.5, 16.2, 24.
8, 27.3, 29.0, 39.6, 119.7, 127.0, 152.9;
¹¹⁹ Sn { ¹ H} -NMR (186 MHz, CDCl ₃ ) δ: −45.8.

Example 7
The reaction was conducted in the same manner as in Example 1 except that 2-tributylstannylethynylethyl ether was used in place of tributyl (octynyl) tin. As a result, the conversion was 100% and 1-ethoxy-1-tributylstannylethylene was recovered. Obtained at a rate of 65%.

1-Ethoxy-1-tributylstannylethylene: yellow oily substance
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.85-0.91 (m, 15H)
, 1.21 (t, J = 6.9 Hz, 3H), 1.30 (sext, J = 7.2 Hz, 6H), 1.45-1.56 (m, 6H), 3.77 (q, J = 7.2 Hz, 2H), 4.50 (d, J = 7.2 Hz, 1H), 6.77 (d, J = 7.2 Hz, 1H);
¹³ C-NMR (75 MHz, CDCl ₃ ) δ: 9.9, 13.6, 15.2, 27.
2, 29.1, 66.7, 97.7, 157.2;
¹¹⁹ Sn { ¹ H} -NMR (186 MHz, CDCl ₃ ) δ: −49.9;
Elemental analysis (C ₁₆ H ₃₄ OSn)
Calculated C, 53.21; H, 9.49
Found C, 53.48; H, 9.33.

Example 8
N, N-dimethyl-2- (diphenylphosphino) phenylmethylamine (10 mol%, 0.04 mmol) was used instead of tributylphosphine, toluene was used as a solvent, and tributyl (octynyl) tin was used instead of tributyl (octynyl) tin. The reaction was conducted in the same manner as in Example 1 except that phenylethynyl) tin was used and the reaction time was 4 hours. As a result, 100% conversion and 1-phenyl-1-tributylstannylethylene were obtained in a yield of 88%. It was.

1-phenyl-1-tributylstannylethylene: yellow oily substance
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.86 (t, J = 7.2 Hz, 9
H), 0.97 (t, J = 8.1 Hz, 6H), 1.29 (sext, J = 7.2 Hz, 6H), 1.43-1.54 (m, 6H), 5.42 ( d, J = 2.4 Hz, 1H), 6.03 (d, J = 2.4 Hz, 1H), 7.15-7.22 (m, 3H), 7.26-7.32 (m, 2H) );
¹³ C-NMR (75 MHz, CDCl ₃ ) δ: 10.1, 13.5, 27.2, 28
. 9, 126.3, 126.4, 126.9, 128.3, 146.5, 154.8;
¹¹⁹ Sn { ¹ H} -NMR (186 MHz, CDCl ₃ ) δ: −40.1.

Example 9
The reaction was conducted in the same manner as in Example 8 except that tributyl (4-methoxyphenylethynyl) tin was used instead of tributyl (phenylethynyl) tin. As a result, the conversion was 100%, and 1- (4-methoxyphenyl)- 1-Tributylstannylethylene was obtained with a yield of 81%.

1- (4-Methoxyphenyl) -1-tributylstannylethylene: yellow oily substance
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.88 (t, J = 7.2 Hz, 9
H), 0.99 (t, J = 8.1 Hz, 6H), 1.32 (sext, J = 7.2 Hz, 6H), 1.46-1.56 (m, 6H), 3.82 ( s, 3H), 5.35 (d, J = 2.4 Hz, 1H), 6.02 (d, J = 2.4 Hz, 1H), 6.86 (d, J = 8.7 Hz, 2H), 7.15 (d, J = 8.4 Hz, 2H);
¹³ C-NMR (75 MHz, CDCl ₃ ) δ: 10.1, 13.5, 27.2, 28
. 9, 55.2, 113.8, 125.3, 127.5, 138.8, 153.7, 158.5;
¹¹⁹ Sn { ¹ H} -NMR (186 MHz, CDCl ₃ ) δ: −40.3.

Example 10
The reaction was conducted in the same manner as in Example 8 except that tributyl (4-trifluoromethylphenylethynyl) tin was used instead of tributyl (phenylethynyl) tin. As a result, the conversion was 100%, and 1- (4-trifluoro Methylphenyl) -1-tributylstannylethylene in 25% yield and 2- (4-trifluoromethylphenyl) -1-tributylstannylethylene in 53% yield (trans / cis = 58/42) Obtained.

1- (4-trifluoromethylphenyl) -1-tributylstannylethylene: yellow oily substance
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.86 (t, J = 7.2 Hz, 9
H), 0.97 (t, J = 8.1 Hz, 6H), 1.29 (sext, J = 7.2 Hz, 6H), 1.42-1.53 (m, 6H), 5.50 ( d, J = 2.4 Hz, 1H), 6.03 (d, J = 2.4 Hz, 1H), 7.22 (d, J = 8.1 Hz, 2H), 7.54 (d, J = 8) .1Hz, 2H);
Elemental analysis (C ₂₁ H ₃₃ F ₃ Sn)
Calculated C, 54.69; H, 7.21
Found C, 54.57; H, 7.055.

Example 11
The reaction was conducted in the same manner as in Example 8 except that tributyl (4-bromophenylethynyl) tin was used instead of tributyl (phenylethynyl) tin. As a result, the conversion was 100%, and 1- (4-bromophenyl)- 1-Tributylstannylethylene was obtained with a yield of 55%.

1- (4-Bromophenyl) -1-tributylstannylethylene: yellow oily substance
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.86 (t, J = 7.2 Hz, 9
H), 0.96 (t, J = 8.1 Hz, 6H), 1.29 (sext, J = 7.2 Hz, 6H), 1.42-1.52 (m, 6H), 5.43 ( d, J = 2.4 Hz, 1H), 6.00 (d, J = 2.4 Hz, 1H), 7.00-7.04 (m, 2H), 7.41 (d, J = 8.7 Hz) , 2H);
¹³ C-NMR (75 MHz, CDCl ₃ ) δ: 10.1, 13.5, 27.2, 28
. 9, 120.1, 127.5, 128.0, 131.4, 145.6, 153.8;
¹¹⁹ Sn { ¹ H} -NMR (186 MHz, CDCl ₃ ) δ: −38.6.

Example 12
When reacted in the same manner as in Example 8 except that tributyl (3-thienylethynyl) tin was used instead of tributyl (phenylethynyl) tin, the conversion was 100% and 1- (3-thienyl) -1- Tributylstannylethylene was obtained with a yield of 65%.

1- (3-Thienyl) -1-tributylstannylethylene: yellow oily substance
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.87 (t, J = 7.2 Hz, 9
H), 0.99 (t, J = 8.1 Hz, 6H), 1.30 (sext, J = 7.2 Hz, 6H), 1.44-1.53 (m, 6H), 5.36 ( d, J = 2.4 Hz, 1H), 6.12 (d, J = 2.4 Hz, 1H), 6.97 (dd, J = 3.0, 1.2 Hz, 1H), 7.10 (dd , J = 5.1, 1.2 Hz, 1H), 7.25 (dd, J = 5.1, 3.0 Hz, 1H);
¹³ C-NMR (75 MHz, CDCl ₃ ) δ: 10.2, 13.4, 27.2, 29
. 0, 120.0, 125.4, 125.8, 126.0, 147.7;
¹¹⁹ Sn { ¹ H} -NMR (186 MHz, CDCl ₃ ) δ: −39.4.

Example 13
The reaction was conducted in the same manner as in Example 1 except that 1,4-bis (tributylstannyl) -1,3-butadiyne was used in place of tributyl (octynyl) tin and the reaction time was 16 hours. Conversion of 100%, 2,4-bis (tributylstannyl) but-1-ene-3-yne in a yield of 38%, and 2,3-bis (tributylstannyl) -1,3-butadiene in yield. Obtained at a rate of 2%.

2,4-bis (tributylstannyl) but-1-ene-3-yne: yellow oily substance
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.89 (t, J = 7.2 Hz, 9
H), 0.90 (t, J = 7.2 Hz, 9H), 0.98-1.04 (m, 12H), 1.25-1.40 (m, 12H), 1.45-1. 61 (m, 12H), 6.50 (s, 2H).

Example 14
The reaction was carried out in the same manner as in Example 2 except that deuterium was used instead of light hydrogen. As a result, the conversion was 100% and 1,1-dideuterio-2-tributylstannyl-1-octene was obtained in a yield of 71%. Was obtained. When the D atom content of the product was estimated from the measurement result of ¹ H-NMR, it was 99% or more.

1,1-dideuterio-2-tributylstannyl-1-octene: yellow oily substance
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.85-0.91 (m, 18H)
1.25-1.54 (m, 20H), 2.23 (t, J = 7.5 Hz, 2H);
¹³ C-NMR (75 MHz, CDCl ₃ ) δ: 9.4, 13.6, 14.0, 22.
6, 27.3, 28.9, 29.0, 29.6, 31.7, 41.2, 124.0, 155.7;
¹¹⁹ Sn { ¹ H} -NMR (186 MHz, CDCl ₃ ) δ: −47.5.

Example 15
The reaction was conducted in the same manner as in Example 1 except that deuterium was used instead of light hydrogen. As a result, the conversion was 100%, and 1,1-dideuterio-2-tributylstannyl-1-octene was 87% in yield. Was obtained. The content of D atoms in the product was 97%.

Example 16
The reaction was conducted in the same manner as in Example 8 except that deuterium was used in place of light hydrogen. As a result, the conversion was 100%, and 2,2-dideterio-1-phenyl-1-tributylstannylethylene had a yield of 70. %. The content of D atoms in the product was 96%.

2,2-dideuterio-1-phenyl-1-tributylstannylethylene: yellow oily substance
¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.86 (t, J = 7.2 Hz, 9
H), 0.97 (t, J = 8.1 Hz, 6H), 1.29 (sext, J = 7.2 Hz, 6H), 1.43-1.54 (m, 6H), 7.15- 7.22 (m, 3H), 7.26-7.32 (m, 2H);
¹³ C-NMR (75 MHz, CDCl ₃ ) δ: 10.1, 13.5, 27.2, 28
. 9, 126.3, 126.4, 126.9, 128.3, 146.5, 154.5;
¹¹⁹ Sn { ¹ H} -NMR (186 MHz, CDCl ₃ ) δ: -39.6.

Claims (8)

The following formula (1a)

(Wherein, X ¹ and X ² represents a water MotoHara element, R ¹ represents an alkyl group or an aryl group, R ² has the A bromide group, and N- substituted amides selected substituents from the group Alkyl group; linear or branched C _1-6 alkyl group, linear or branched halo C _1-6 alkyl group, hydroxyl group, carboxyl group, linear or branched C _1-6 alkoxy A C _6-10 aryl group having at least one substituent selected from a carbonyl group, an amide group, and an N-substituted amide group ; a 5- or 6-membered heterocyclic group containing at least one sulfur atom as a constituent atom of the ring; A condensed heterocyclic group obtained by condensing a 5- or 6-membered heterocyclic group containing at least one sulfur atom as a ring constituent atom and a hydrocarbon ring ; or a group R ¹ ₃ Sn—C≡C— (R ¹ is the same as above ) shows a. organotin represented by) Compounds. In the presence of a catalyst composed of a transition metal element, a hydrogen molecule or deuterium molecule represented by the following formula (3) is reacted with an alkynyltin compound represented by the following formula (2), and the following formula (1) ) The manufacturing method of the organotin compound represented by this .

[Wherein, R ^1a , R ^1b , R ^1c and R ^2a are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, a heterocyclic group, an alkoxy group, or the following formula ( Group represented by 4)

(R ^1a , R ^1b and R ^1c are the same as above), and the alkyl group, alkenyl group, aryl group, aralkyl group, heterocyclic group or alkoxy group may have a substituent, and X ¹ and X ² is the same or different and represents a hydrogen atom or a deuterium atom]   The production method according to claim 2, wherein the transition metal element is at least one element selected from Group 4 elements of the periodic table to Group 11 elements of the periodic table.   The production method according to claim 2, wherein the reaction is performed in the presence of a compound containing at least one element selected from Group 15 elements of Periodic Table and Group 16 elements of Periodic Table. A catalyst comprising at least one transition metal element selected from periodic table group 6 element and the periodic table group 8 element, according to claim 2, wherein the reaction in the presence of a compound containing the Group 15 element Manufacturing method. In order to produce an organotin compound represented by the following formula (1) by reacting a hydrogen molecule or deuterium molecule represented by the following formula (3) with an alkynyltin compound represented by the following formula (2). A catalyst composed of a transition metal element.

[Wherein, R ^1a , R ^1b , R ^1c and R ^2a are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aralkyl group, a heterocyclic group, an alkoxy group, or the following formula ( Group represented by 4)

(R ^1a , R ^1b and R ^1c are the same as above), and the alkyl group, alkenyl group, aryl group, aralkyl group, heterocyclic group or alkoxy group may have a substituent, and X ¹ and X ² is the same or different and represents a hydrogen atom or a deuterium atom]   Furthermore, the catalyst of Claim 6 containing the compound containing at least 1 type of element selected from the periodic table 15 group element and the periodic table 16 group element. At least one transition with a compound containing a metal element, the catalyst according to claim 6, characterized in that is composed of a compound containing the Group 15 element selected from the group 6 element and the periodic table group 8 element periodic table.