JPH01233237A - Production of acetylene compound - Google Patents
Production of acetylene compoundInfo
- Publication number
- JPH01233237A JPH01233237A JP6121388A JP6121388A JPH01233237A JP H01233237 A JPH01233237 A JP H01233237A JP 6121388 A JP6121388 A JP 6121388A JP 6121388 A JP6121388 A JP 6121388A JP H01233237 A JPH01233237 A JP H01233237A
- Authority
- JP
- Japan
- Prior art keywords
- alkyl halide
- alkynyl
- inert solvent
- reaction
- alkali metal
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- -1 acetylene compound Chemical class 0.000 title claims description 14
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims description 12
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 150000001350 alkyl halides Chemical class 0.000 claims abstract description 21
- 150000003983 crown ethers Chemical class 0.000 claims abstract description 13
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 13
- 239000012442 inert solvent Substances 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 abstract description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract 2
- 229910000765 intermetallic Inorganic materials 0.000 abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 33
- 229910052708 sodium Inorganic materials 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 7
- 239000000725 suspension Substances 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000007983 Tris buffer Substances 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 6
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 5
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 3
- LSXKDWGTSHCFPP-UHFFFAOYSA-N 1-bromoheptane Chemical compound CCCCCCCBr LSXKDWGTSHCFPP-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- VWWMOACCGFHMEV-UHFFFAOYSA-N dicarbide(2-) Chemical compound [C-]#[C-] VWWMOACCGFHMEV-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- XNMQEEKYCVKGBD-UHFFFAOYSA-N 2-butyne Chemical compound CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- YSSSPARMOAYJTE-UHFFFAOYSA-N dibenzo-18-crown-6 Chemical compound O1CCOCCOC2=CC=CC=C2OCCOCCOC2=CC=CC=C21 YSSSPARMOAYJTE-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- CAYDJHOYFLLLLM-UHFFFAOYSA-N 2-[2-(2-ethoxyethoxy)ethoxy]-n,n-bis[2-[2-(2-ethoxyethoxy)ethoxy]ethyl]ethanamine Chemical compound CCOCCOCCOCCN(CCOCCOCCOCC)CCOCCOCCOCC CAYDJHOYFLLLLM-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- XBVBXOUDNYOAQZ-UHFFFAOYSA-N C(#CCC)[Na] Chemical compound C(#CCC)[Na] XBVBXOUDNYOAQZ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 125000004036 acetal group Chemical group 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910001508 alkali metal halide Inorganic materials 0.000 description 1
- 150000008045 alkali metal halides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- UNTITLLXXOKDTB-UHFFFAOYSA-N dibenzo-24-crown-8 Chemical compound O1CCOCCOCCOC2=CC=CC=C2OCCOCCOCCOC2=CC=CC=C21 UNTITLLXXOKDTB-UHFFFAOYSA-N 0.000 description 1
- QMLGNDFKJAFKGZ-UHFFFAOYSA-N dicyclohexano-24-crown-8 Chemical compound O1CCOCCOCCOC2CCCCC2OCCOCCOCCOC2CCCCC21 QMLGNDFKJAFKGZ-UHFFFAOYSA-N 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 150000002497 iodine compounds Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000007867 post-reaction treatment Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/325—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom
- C07C1/328—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a metal atom the hetero-atom being an alkali metal atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明はアセチレン化合物の新規な製造方法に間する。[Detailed description of the invention] (Industrial application field) The present invention provides a novel method for producing acetylene compounds.
（従来の技術）
従来、アセチレン化合物の製造方法としては例えば下記
一般式（ＩＩ）で示される１−アルキニルアルカリ金属
化合物と下記一般式（ｍ）で示されるハロゲン化アルキ
ルとを液体アンモニア中で反応させて下記一般式（ＩＶ
）で示されるアセチレン化合物を得る方法が知られてい
る。(Prior Art) Conventionally, as a method for producing an acetylene compound, for example, a 1-alkynyl alkali metal compound represented by the following general formula (II) and an alkyl halide represented by the following general formula (m) are reacted in liquid ammonia. Then, the following general formula (IV
) is known.
Ｒ２Ｃ＝ＣＭ＋Ｒ３Ｘ−）Ｒ２Ｃ５＝ＣＲ３＋ＭＸ（Ｉ
Ｉ） （ｍ） （ＩＶ）（式中、Ｒ２は水
素原子又は有機残基、Ｍはアルカリ金属、Ｒ３は有機残
基、Ｘはハロゲンを示す。）しかしながら、この方法は
アンモニアが毒性がある上、可燃性であり、また長鎖の
アセチレン化合物を合成するためにはハロゲン化アルキ
ルの溶解度を増加させる必要があり加圧下に反応させな
ければならないなど工業的に実施するには多くの問題点
があった。R2C=CM+R3X-)R2C5=CR3+MX(I
I) (m) (IV) (In the formula, R2 is a hydrogen atom or an organic residue, M is an alkali metal, R3 is an organic residue, and X is a halogen.) However, this method is difficult because ammonia is toxic. However, it is flammable, and in order to synthesize long-chain acetylene compounds, it is necessary to increase the solubility of the alkyl halide and the reaction must be carried out under pressure.There are many problems in implementing it industrially. there were.
そこで液体アンモニアに代わる溶媒として種々の有機溶
媒を用いる方法が検討されてきた。例えば、Ｎ、 Ｎ
−ジメチルホルムアミドを溶媒とする方法（Ｅ、Ｆ、Ｊ
ｅｎｎｙらＡｎｇｅｗ、Ｃｈｅｍ、 エ、２４５（１９
５９））、Ｎ、 Ｎ−ジメチルホルムアミド、・ Ｎ
、 Ｎ−ジメチルアセトアミドあるいはへキサメチル
ホスホルトリアミドなどの極性溶媒とキシレンの如き炭
化水素系溶媒との混合溶媒系を用いる方法（Ｔ、Ｆ。Therefore, methods using various organic solvents as solvents in place of liquid ammonia have been investigated. For example, N, N
-Method using dimethylformamide as a solvent (E, F, J
enny et al. Angew, Chem., 245 (19
59)), N, N-dimethylformamide, ・N
, A method using a mixed solvent system of a polar solvent such as N-dimethylacetamide or hexamethylphosphortriamide and a hydrocarbon solvent such as xylene (T, F).
Ｒｕｔｌｅｄｇｅ、Ｊ、Ｏｒｇ、Ｃｈｅｍ、、、ｌ、
８４０（１９５９））、ジメチルスルホキシドを溶媒と
する方法（Ｊ、Ｋｒ１ｚら、Ｔｅｔｒａｈｅｄｒｏｎ
Ｌｅｔｔｅｒｓ、Ｌ９ｆｉＭ、２８８１）などが報告さ
れている。これらの方法は前記一般式（ｎ）のＲ２が水
素原子、すなわち無置換のアセチレンのアセチリドの場
合にはよい結果をあたえるが、Ｒが例えばアルキル基の
ような有機残基である置換アセチレンのアセチリドの場
合には満足な収率が得られていないという問題点があっ
た。例えば、ｌ−プロピニルナトリウムの場合について
種々の溶媒を検討した結果、ジメチルスルホキシドを用
いた最良の条件下でも収率はたかだか３６％であった（
Ｗ−Ｎ、Ｓｍ１ｔｈら、 Ｊ、Ｏｒｇ−Ｃｈｅｍ、 Ｊ
ｌ、３５８８（１９７３））。Rutledge, J, Org, Chem,,,l,.
840 (1959)), a method using dimethyl sulfoxide as a solvent (J, Kr1z et al., Tetrahedron
Letters, L9fiM, 2881), etc. have been reported. These methods give good results when R2 in the general formula (n) is a hydrogen atom, that is, an acetylide of unsubstituted acetylene; In this case, there was a problem that a satisfactory yield was not obtained. For example, in the case of l-propynyl sodium, various solvents were investigated, and even under the best conditions using dimethyl sulfoxide, the yield was only 36% (
W-N, Smlth et al., J., Org-Chem, J.
I, 3588 (1973)).
（発明が解決しようとする課題）
本発明の目的は、広範囲の１−アルキニルアルカリ金属
化合物（すなわち、前記一般式（ｎ）のＲ２が水素原子
又は有機残基である該化合物）のアルキル化に適用する
ことができ、更には対応するアセチレン化合物を高収率
で、かつ、安全な方法で得ることが出来るようなアセチ
レン化合物の製造方法を提供することにある。(Problems to be Solved by the Invention) The purpose of the present invention is to alkylate a wide range of 1-alkynyl alkali metal compounds (i.e., compounds in which R2 in the general formula (n) is a hydrogen atom or an organic residue). It is an object of the present invention to provide a method for producing an acetylene compound, which can be applied and furthermore, the corresponding acetylene compound can be obtained in a high yield and in a safe manner.
（課題を解決するための手段）
本発明のかかる目的は、１−アルキニルアルカリ金属化
合物とハロゲン化アルキルとを（１）不活性溶媒及びク
ラウンエーテル又は（２）不活性溶媒及び下記一般式（
ｒ）で示される三級アミンの存在下に反応させることに
よって達成される。(Means for Solving the Problems) This object of the present invention is to combine a 1-alkynyl alkali metal compound and an alkyl halide with (1) an inert solvent and a crown ether or (2) an inert solvent and the following general formula (
This is achieved by reacting in the presence of a tertiary amine represented by r).
Ｎ ［（ＣＨ２ＣＲ２０）ｎＲ’コ ３ （■
）（式中、Ｒ１はアルキル基を示す。ｎは２〜４の整数
を示す。）
本発明において用いられる１−アルキニルアルカリ金属
化合物は下記一般式（■）で示される。N [(CH2CR20)nR'ko 3 (■
) (In the formula, R1 represents an alkyl group. n represents an integer of 2 to 4.) The 1-alkynyl alkali metal compound used in the present invention is represented by the following general formula (■).
Ｒ２ＣミＣＭ （Ｔｌ）
式中、Ｒ２は水素原子又は有機残基を示す。かかる有機
残基は反応に不活性なものであれば特に限定されず、具
体例としては、メチル基、エチル基、プロピル基、ブチ
ル基、ペンチル基、ヘキシル基、ヘプチル基、イソプロ
ピル基、イソブチル基、セカンダリ−ブチル基、ターシ
ャリ−ブチル基などのアルキル基、フェニル基、アルキ
ル基置換フェニル基、ナフチル基、メトキシフェニル基
のようなアルコキシ基置換フェニル基、ピリジル基など
のアリール基、ざらにはこれらにビニル基、プロペニル
基、イソプロペニル基、ブテニル基、エチニル基、ベン
ジル基、メトキシ基、エトキシ基などのアルコキシ基や
アセタール基などの不飽和結合やエーテル結合を有する
置換基が結合したものが例示される。R2CmiCM (Tl) In the formula, R2 represents a hydrogen atom or an organic residue. Such organic residues are not particularly limited as long as they are inert to the reaction, and specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, isopropyl, and isobutyl groups. , secondary butyl group, alkyl group such as tertiary butyl group, phenyl group, alkyl group substituted phenyl group, naphthyl group, alkoxy group substituted phenyl group such as methoxyphenyl group, aryl group such as pyridyl group, etc. Examples include a substituent having an unsaturated bond or an ether bond such as an alkoxy group such as a vinyl group, propenyl group, isopropenyl group, butenyl group, ethynyl group, benzyl group, methoxy group, or ethoxy group or an acetal group. be done.
式中、Ｍはアルカリ金属を示し、例えば、ナトリウム、
カリウムなどが挙げられる。In the formula, M represents an alkali metal, for example, sodium,
Examples include potassium.
一方、ハロゲン化アルキルは下記一般式（ｍ）で示され
る。On the other hand, halogenated alkyl is represented by the following general formula (m).
Ｒ３Ｘ （ＩＩｌ、）
式中Ｒ３は前述のＲ２と同様の有機残基を示し、叉、場
合によっては塩素、弗素といったハロゲンを含んでいて
も差し支えない。R 3
式中、Ｘはハロゲンを示し、具体例としては塩素、臭素
、沃素等が挙げられ、なかでも、臭素、沃素が好適であ
るが、塩素の場合も沃化ナトリウムなどの沃素化合物と
併用することによって好適に実施することができる。In the formula, X represents halogen, and specific examples include chlorine, bromine, iodine, etc. Among them, bromine and iodine are preferred, but in the case of chlorine, it may be used in combination with an iodine compound such as sodium iodide. It can be suitably implemented by.
本発明において用いられる不活性溶媒は１−アルキニル
アルカリ金属化合物やハロゲン化アルキルと反応するも
のでなければ特に限定されない。The inert solvent used in the present invention is not particularly limited as long as it does not react with the 1-alkynyl alkali metal compound or the alkyl halide.
例えば、ベンゼン、トルエン、キシレンなどの芳香族炭
化水素系溶媒、ヘプタン、オクタンなどの脂肪族炭化水
素系溶媒、テトラヒドロフラン、ジメトキシエタン、ジ
ェトキシエタン、ジエチレングリコールジメチルエーテ
ルなどのエーテル系溶媒、トリメチルアミン、トリエチ
ルアミン、ジメチルアニリン、ピリジンなどの含窒素系
溶媒などが挙げられる。これらの中でも、反応後の処理
を簡便に実施しうる点で、副生ずるハロゲン化アルカリ
金属を溶解しない炭化水素系溶媒を使用することが好ま
しい。For example, aromatic hydrocarbon solvents such as benzene, toluene, and xylene, aliphatic hydrocarbon solvents such as heptane and octane, ether solvents such as tetrahydrofuran, dimethoxyethane, jetoxyethane, and diethylene glycol dimethyl ether, trimethylamine, triethylamine, dimethylaniline, Examples include nitrogen-containing solvents such as pyridine. Among these, it is preferable to use a hydrocarbon solvent that does not dissolve the alkali metal halide produced as a by-product, since post-reaction treatments can be carried out easily.
又、炭化水素系あるいはエーテル系溶媒中でアルカリ金
属化合物ディスバージョンとアセチレン化合物を反応さ
せて１−アルキニルアルカリ金属化合物を調製し、直接
これにクラウンエーテル又は三級アミンとハロゲン化ア
ルキルとを加えて反応させることが有利である。Alternatively, a 1-alkynyl alkali metal compound is prepared by reacting an alkali metal compound dispersion with an acetylene compound in a hydrocarbon or ether solvent, and a crown ether or tertiary amine and an alkyl halide are directly added thereto. It is advantageous to react.
本発明において用いられるクラウンエーテルの基本骨格
は下記一般的（Ｖ）で示される。The basic skeleton of the crown ether used in the present invention is shown in general (V) below.
式中、ｍは４以上、好ましくは４〜１０の整数を示す。In the formula, m represents an integer of 4 or more, preferably 4 to 10.
また、エチレン鎖の水素は炭化水素残基やハロゲンで適
宜置換されていてもよい。具体例としては、１５−クラ
ウン−５，１８−クラウン−６、ジベンゾ−１８−クラ
ウン−６、ジベンゾ−２４−クラウン−８、ジシクロへ
キサノー１８−クラウン−６、ジシクロヘキサノ−２４
−クラウン−８などが挙げられる。Further, hydrogen in the ethylene chain may be appropriately substituted with a hydrocarbon residue or a halogen. Specific examples include 15-crown-5,18-crown-6, dibenzo-18-crown-6, dibenzo-24-crown-8, dicyclohexano-18-crown-6, dicyclohexano-24
-Crown-8 etc.
一方、本発明において用いられる三級アミンは下記一般
的（１）で示される。On the other hand, the tertiary amine used in the present invention is represented by general (1) below.
Ｎ ［（ＣＨ２ＣＨ２０）ｎＲ’］ ３ （Ｉ）式中
、Ｒ１はアルキル基を示す。また、ｎは２〜４の整数を
示す。具体例としては、トリス（３゜６−シオキサヘブ
チル）アミン、トリス（３，６−シオキサオクチル）ア
ミン、トリス（３，６−シオキサノニル）アミン、トリ
ス（３，６−シオキサデシル）アミン、トリス（３，６
，９−）リオキサデシル）アミン、トリス（３，６，９
−トリオキサウンデシル）アミンなどが挙げられる。N [(CH2CH20)nR'] 3 (I) In the formula, R1 represents an alkyl group. Moreover, n represents an integer of 2 to 4. Specific examples include tris(3゜6-thioxahebutyl)amine, tris(3,6-thioxaoctyl)amine, tris(3,6-thioxanonyl)amine, tris(3,6-thioxadecyl)amine, tris(3 ,6
,9-)lioxadecyl)amine, tris(3,6,9
-trioxaundecyl)amine, and the like.
これらは単独で使用しても、２種類以上混合して用いて
もよい。These may be used alone or in combination of two or more.
１−アルキニルアルカリ金属化合物とハロゲン化アルキ
ルとの反応は、不活性溶媒とクラウンエーテル及び／又
は三級アミンの存在下に実施される。ハロゲン化アルキ
ルの使用量は、１−アルキニルアルカリ金属化合物１モ
ルに対し０．５〜１．５モルが適当である。不活性溶媒
の量は、攪拌が可能であれば任意で差し支えないが、ハ
ロゲン化アルキルに対し１〜２０重量部用いるとよい。The reaction between the 1-alkynyl alkali metal compound and the alkyl halide is carried out in the presence of an inert solvent and a crown ether and/or a tertiary amine. The appropriate amount of the alkyl halide to be used is 0.5 to 1.5 moles per mole of the 1-alkynyl alkali metal compound. The amount of the inert solvent may be arbitrary as long as stirring is possible, but it is preferably used in an amount of 1 to 20 parts by weight based on the alkyl halide.
クラウンエーテルの使用量は１−アルキニルアルカリ金
属化合物に対し帆ｌ〜３０モル％、好ましくは１〜１０
モル％である。又、三級アミンの使用量は１−アルキニ
ルアルカリ金属化合物に対し１〜３０モル％、好ましく
は５〜２０モル％である。The amount of crown ether used is 1 to 30 mol%, preferably 1 to 10% by mole based on the 1-alkynyl alkali metal compound.
It is mole%. Further, the amount of the tertiary amine used is 1 to 30 mol%, preferably 5 to 20 mol%, based on the 1-alkynyl alkali metal compound.
本発明においては不活性溶媒とクラウンエーテル及び／
又は三級アミンの存在下に反応を実施することが重要で
あり、反応温度や反応時間などの条件は適宜選択すれば
よい。例えば、反応温度は溶媒の還流温度であればよい
が、通常は、８０〜２００℃であり、また、反応時間は
数分〜数十時間である。In the present invention, an inert solvent, a crown ether and/or
Alternatively, it is important to carry out the reaction in the presence of a tertiary amine, and conditions such as reaction temperature and reaction time may be appropriately selected. For example, the reaction temperature may be any reflux temperature of the solvent, but is usually 80 to 200°C, and the reaction time is several minutes to several tens of hours.
１−アルキニルアルカリ金属化合物とハロゲン化アルキ
ルとの反応させ方としては、ｌ−アルキニルアルカリ金
属化合物の懸濁液とハロゲン化アルキルおよびクラウン
エーテル、もしくは、ハロゲン化アルキルおよび三級ア
ミンを混合しておいてから所定の温度に昇温するのが一
般的であるが、所定の温度に保たれた１−アルキニルア
ルカリ金属化合物のｔ［液とクラウンエーテル、もしく
は、１−アルキニルアルカリ金属化合物の懸濁液と三級
アミンの溶液にハロゲン化アルキルを滴下してもよい。To react a 1-alkynyl alkali metal compound and an alkyl halide, mix a suspension of the 1-alkynyl alkali metal compound, an alkyl halide and a crown ether, or an alkyl halide and a tertiary amine. It is common to raise the temperature to a predetermined temperature after the temperature is set, but if the t[liquid and crown ether of the 1-alkynyl alkali metal compound maintained at a predetermined temperature or a suspension of the 1-alkynyl alkali metal compound The alkyl halide may be added dropwise to a solution of tertiary amine and tertiary amine.
又は、ハロゲン化アルキルとクラウンエーテル、もしく
は、ハロゲン化アルキルと三級アミンの溶液に１−アル
キニルアルカリ金属化合物の懸濁液を滴下しても差し支
えない。Alternatively, a suspension of a 1-alkynyl alkali metal compound may be added dropwise to a solution of an alkyl halide and a crown ether, or an alkyl halide and a tertiary amine.
（発明の効果）
かくして本発明によれば無置換アセチレンのアセチリド
だけでなく置換アセチレンのアセチリドの場合も高収率
で対応するアセチレン化合物を得ることができ、また使
用する溶媒の安全性が高いなど多くの利点を有する。(Effects of the Invention) Thus, according to the present invention, the corresponding acetylene compound can be obtained in high yield not only in the case of acetylide of unsubstituted acetylene but also in the case of acetylide of substituted acetylene, and the solvent used is highly safe. Has many advantages.
（実施例）
以下に実施例を挙げて本発明をさらに具体的に説明する
。なお、実施例、比較例及び参考例中の部及び％は特に
断わりのない限り重量基準である。(Example) The present invention will be described in more detail with reference to Examples below. Note that parts and percentages in Examples, Comparative Examples, and Reference Examples are based on weight unless otherwise specified.
参考例 ｌ−ブチニルナトリウムの調製オートクレーブ
中にナトリウムディスバージョン（トルエン／ナトリウ
ム金属（重量比） ＝２／１）３４．５部を仕込んだの
ち、２−ブチン５８部およびトルエン１２７部を仕込み
、窒素雰囲気下、１００℃で２時間攪拌してｌ−ブチニ
ルナトリウムのトルエン懸濁液を合成した。Reference Example Preparation of sodium l-butynyl After charging 34.5 parts of sodium dispersion (toluene/sodium metal (weight ratio) = 2/1) into an autoclave, 58 parts of 2-butyne and 127 parts of toluene were charged. The mixture was stirred at 100° C. for 2 hours under a nitrogen atmosphere to synthesize a suspension of l-butynyl sodium in toluene.
実施例１
還流冷却器を備えた５０艷の三角フラスコに参考例で得
たｌ−ブチニルナトリウムを０．０３５モル含むトルエ
ン懸濁液１２．５ｇ、第１表に示す所定のハロゲン化ア
ルキル、トルエン７．５ｇおよび１８−クラウン−６を
０．５ｇ入れ、ホットプレート付きのマグネチックスタ
ーシー上で４時間攪拌下に還流させた。反応後、内部標
準物質としてｎ−ウンデカンを加えて攪拌した後、固形
分を遠心分離して除き上澄み液をガスクロマトグラフィ
ーにより分析した結果、ハロゲン化アルキルの転化率及
び３−ウンデシンの収率は第１表に示す通りであった。Example 1 In a 50-length Erlenmeyer flask equipped with a reflux condenser, 12.5 g of the toluene suspension containing 0.035 mol of l-butynyl sodium obtained in Reference Example, a predetermined alkyl halide shown in Table 1, 7.5 g of toluene and 0.5 g of 18-crown-6 were added, and the mixture was stirred and refluxed for 4 hours on a magnetic starboard equipped with a hot plate. After the reaction, n-undecane was added as an internal standard substance and stirred, and the solid content was removed by centrifugation and the supernatant liquid was analyzed by gas chromatography. As a result, the conversion rate of alkyl halide and the yield of 3-undecine were determined. It was as shown in Table 1.
尚、第１表の実験番号１３は実験操作において４時間攪
拌下に還流させた後、ヨウ化ナトリウム１ｇを添加しさ
らに８時間還流を続けたときの結果である。Experiment No. 13 in Table 1 shows the results obtained when the mixture was refluxed with stirring for 4 hours, then 1 g of sodium iodide was added, and reflux was continued for an additional 8 hours.
又、比較のため１８−クラウン−６を使用しない他は実
験番号１１と全く同様にして反応を行ったところｌ−ブ
ロモヘプタンの転化率は３％、３−ウンデシンの収率は
１．５％であった。For comparison, the reaction was carried out in exactly the same manner as in Experiment No. 11, except that 18-crown-6 was not used. The conversion rate of l-bromoheptane was 3%, and the yield of 3-undecine was 1.5%. Met.
第１表
実施例２
還流冷却器を備えた５０艷の三角フラスコに参考例で得
たｌ−ブチニルナトリウムを０．０２８モル含むトルエ
ン懸濁液ｔｏ、ｏ ｇ、１−ブロモへブタン５．０ｇ、
トルエン１０．０ｇおよび第２表に示すクラウンエーテ
ル０．５ｇを入れ、ホットプレート付きのマグネチック
スターシー上で４時間攪拌下に還流させた。反応後、実
施例１に準じて１−ブロモへブタンの転化率及び３−ウ
ンデシンの収率をガスクロマトグラフィーにより測定し
た。結果を第２表に示す。Table 1 Example 2 A toluene suspension containing 0.028 mol of 1-butynyl sodium obtained in Reference Example was placed in a 50-length Erlenmeyer flask equipped with a reflux condenser to 0 g of 1-bromohebutane. 0g,
10.0 g of toluene and 0.5 g of crown ether shown in Table 2 were added, and the mixture was stirred and refluxed for 4 hours on a magnetic starboard equipped with a hot plate. After the reaction, the conversion rate of 1-bromohebutane and the yield of 3-undecine were measured by gas chromatography according to Example 1. The results are shown in Table 2.
第２表
実施例３
還流冷却器を備えた。５０艷の三角フラスコに１−ヘブ
チニルナトリウム０．０３５モル、トルエン２０．０
ｇ、１−ブロモブタン３．８０ｇ及び１８−クラウン−
６を０．５ｇ入れ、３時間攪拌下に還流させた。反応後
、実施例１に準じてｌ−ブロモブタンの転化率及び５−
ウンデシンの収率をガスクロマトグラフィーにより測定
したところ、１−ブロモブタンの転化率が９８％、５−
ウンデシンの収率が８５％であった。Table 2 Example 3 A reflux condenser was provided. 0.035 mol of 1-hebutynyl sodium and 20.0 mol of toluene in a 50-length Erlenmeyer flask.
g, 3.80 g of 1-bromobutane and 18-crown-
6 was added thereto, and the mixture was stirred and refluxed for 3 hours. After the reaction, the conversion rate of l-bromobutane and 5-
When the yield of undecine was measured by gas chromatography, the conversion rate of 1-bromobutane was 98%, and the conversion rate of 5-bromobutane was 98%.
The yield of undecine was 85%.
実施例４
還流冷却器を備えた５０−の三角フラスコに参考例で得
たｌ−ブチニルナトリウムを０．０３５モル含むトルエ
ン懸濁液１２．５ ｇ、第３表に示す所定の１−ハロゲ
ン化アルキル、３級アミン１．０ｇ及びトルエン７．５
ｇを入れ、ホットプレート付きのマグネチックスターシ
ー上で所定の時間攪拌下に還流させた。Example 4 In a 50-sized Erlenmeyer flask equipped with a reflux condenser, 12.5 g of the toluene suspension containing 0.035 mol of l-butynyl sodium obtained in Reference Example, and the specified 1-halogen shown in Table 3 were added. alkyl, tertiary amine 1.0g and toluene 7.5g
g was added thereto, and the mixture was refluxed under stirring for a predetermined period of time on a magnetic starsee equipped with a hot plate.
反応後、実施例１に準じて１−ハロゲン化アルキルの転
化率及び３−ウンデシンの収率をガスクロマトグラフィ
ーにより測定した。結果を第３表に示す。After the reaction, the conversion rate of 1-halogenated alkyl and the yield of 3-undecine were measured by gas chromatography according to Example 1. The results are shown in Table 3.
又、比較のためトリス（，３，６−シオキサヘブチル）
アミンを使用しない他は実験番号１１と全く同様にして
反応を行ったところ１−ブロモへブタンの転化率は３％
、３−ウンデシンの収率は１．５％であった。Also, for comparison, tris(,3,6-thioxahebutyl)
The reaction was carried out in exactly the same manner as Experiment No. 11 except that no amine was used, and the conversion rate of 1-bromohebutane was 3%.
, the yield of 3-undecine was 1.5%.
実施例５
還流冷却器を備えた５０ｒｎ！Ｑの三角フラスコに１−
ブチニルナトリウム０．０３５モル、１．２−ジェトキ
シエタン２０．０ｇ、 １−ブロモヘプタン５．０ｇ
及びトリス（３，６−ジオキサへブチル）アミン１．０
ｇを入れ、４時間攪拌下に還流させた。反応後、実施例
１に準じて１−ブロモヘプタンの転化率及び５−ウンデ
シンの収率をガスクロマトグラフィーにより測定したと
ころ、ｌ−ブロモヘプタンの転化率が９８％、５−ウン
デシンの収率が８５％であった。Example 5 50rn equipped with reflux condenser! 1- in the Erlenmeyer flask of Q
Butynyl sodium 0.035 mol, 1,2-jethoxyethane 20.0 g, 1-bromoheptane 5.0 g
and tris(3,6-dioxahebutyl)amine 1.0
g was added thereto, and the mixture was refluxed with stirring for 4 hours. After the reaction, the conversion rate of 1-bromoheptane and the yield of 5-undecine were measured by gas chromatography according to Example 1. The conversion rate of 1-bromoheptane was 98%, and the yield of 5-undecine was 98%. It was 85%.
特許出願人 日本ゼオン株式会社Patent applicant: Zeon Corporation
Claims (2)
アルキルとを反応させてアセチレン化合物を得る方法に
おいて、前記反応を不活性溶媒及びクラウンエーテルの
存在下に行うことを特徴とするアセチレン化合物の製造
方法。(1) A method for producing an acetylene compound by reacting a 1-alkynyl alkali metal compound with an alkyl halide, the method comprising performing the reaction in the presence of an inert solvent and a crown ether.
アルキルとを反応させてアセチレン化合物を得る方法に
おいて、前記反応を不活性溶媒及び下記一般式（ I ）
で示される三級アミンの存在下に行うことを特徴とする
アセチレン化合物の製造方法。 Ｎ［（ＣＨ＿２ＣＨ＿２Ｏ）＿ｎＲ＾１］＿３（ I ）
（式中、Ｒ＾１はアルキル基を示す。ｎは２〜４の整数
を示す。）(2) In a method for obtaining an acetylene compound by reacting a 1-alkynyl alkali metal compound and an alkyl halide, the reaction is carried out using an inert solvent and the following general formula (I).
A method for producing an acetylene compound, characterized in that the method is carried out in the presence of a tertiary amine represented by: N[(CH_2CH_2O)_nR^1]_3(I)
(In the formula, R^1 represents an alkyl group. n represents an integer of 2 to 4.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6121388A JPH01233237A (en) | 1988-03-15 | 1988-03-15 | Production of acetylene compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6121388A JPH01233237A (en) | 1988-03-15 | 1988-03-15 | Production of acetylene compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01233237A true JPH01233237A (en) | 1989-09-19 |
Family
ID=13164697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP6121388A Pending JPH01233237A (en) | 1988-03-15 | 1988-03-15 | Production of acetylene compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01233237A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5162596A (en) * | 1991-02-19 | 1992-11-10 | Shin-Etsu Chemical Co., Ltd. | Z-12-heptadecen-1-yne |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52156803A (en) * | 1976-06-21 | 1977-12-27 | Kuraray Co Ltd | Reaction process |
| JPS59186927A (en) * | 1983-02-18 | 1984-10-23 | ロ−ヌ−プ−ラン・スペシアリテ・シミ−ク | Manufacture of cyclopropane derivatives |
-
1988
- 1988-03-15 JP JP6121388A patent/JPH01233237A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52156803A (en) * | 1976-06-21 | 1977-12-27 | Kuraray Co Ltd | Reaction process |
| JPS59186927A (en) * | 1983-02-18 | 1984-10-23 | ロ−ヌ−プ−ラン・スペシアリテ・シミ−ク | Manufacture of cyclopropane derivatives |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5162596A (en) * | 1991-02-19 | 1992-11-10 | Shin-Etsu Chemical Co., Ltd. | Z-12-heptadecen-1-yne |
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