JPH0140024B2 - - Google Patents
Info
- Publication number
- JPH0140024B2 JPH0140024B2 JP59040184A JP4018484A JPH0140024B2 JP H0140024 B2 JPH0140024 B2 JP H0140024B2 JP 59040184 A JP59040184 A JP 59040184A JP 4018484 A JP4018484 A JP 4018484A JP H0140024 B2 JPH0140024 B2 JP H0140024B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- ruthenium
- reaction
- cyanide
- cyanohydrin
- 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.)
- Expired
Links
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 16
- 229910052707 ruthenium Inorganic materials 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 7
- 125000000962 organic group Chemical group 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 125000003710 aryl alkyl group Chemical group 0.000 claims 1
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 14
- 150000001264 acyl cyanides Chemical class 0.000 description 12
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 9
- 239000002904 solvent Substances 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 6
- -1 α-tetralyl group Chemical group 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000004820 halides Chemical class 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- DHCWLIOIJZJFJE-UHFFFAOYSA-L dichlororuthenium Chemical compound Cl[Ru]Cl DHCWLIOIJZJFJE-UHFFFAOYSA-L 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- GJQBHOAJJGIPRH-UHFFFAOYSA-N benzoyl cyanide Chemical compound N#CC(=O)C1=CC=CC=C1 GJQBHOAJJGIPRH-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007333 cyanation reaction Methods 0.000 description 2
- HBIHVBJJZAHVLE-UHFFFAOYSA-L dibromoruthenium Chemical compound Br[Ru]Br HBIHVBJJZAHVLE-UHFFFAOYSA-L 0.000 description 2
- 239000000539 dimer Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- NNICRUQPODTGRU-UHFFFAOYSA-N mandelonitrile Chemical compound N#CC(O)C1=CC=CC=C1 NNICRUQPODTGRU-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- DCYICVONOLZQJK-UHFFFAOYSA-N (4-chlorophenyl)phosphane Chemical compound PC1=CC=C(Cl)C=C1 DCYICVONOLZQJK-UHFFFAOYSA-N 0.000 description 1
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 description 1
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 238000005643 Gatterman-Koch carbonylation reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AIXAANGOTKPUOY-UHFFFAOYSA-N carbachol Chemical group [Cl-].C[N+](C)(C)CCOC(N)=O AIXAANGOTKPUOY-UHFFFAOYSA-N 0.000 description 1
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- ICPMUWPXCAVOOQ-XCADPSHZSA-N cycloocta-1,3,5-triene Chemical compound C\1C\C=C/C=C\C=C/1 ICPMUWPXCAVOOQ-XCADPSHZSA-N 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-M hydroperoxide group Chemical group [O-]O MHAJPDPJQMAIIY-UHFFFAOYSA-M 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 230000000749 insecticidal effect Effects 0.000 description 1
- 239000000543 intermediate Substances 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
- 150000004715 keto acids Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 239000003921 oil Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WYRXRHOISWEUST-UHFFFAOYSA-K ruthenium(3+);tribromide Chemical compound [Br-].[Br-].[Br-].[Ru+3] WYRXRHOISWEUST-UHFFFAOYSA-K 0.000 description 1
- LJZVDOUZSMHXJH-UHFFFAOYSA-K ruthenium(3+);triiodide Chemical compound [Ru+3].[I-].[I-].[I-] LJZVDOUZSMHXJH-UHFFFAOYSA-K 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Furan Compounds (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明はアシルシアニド類の効率的な製造法に
関し、更に詳しくは、シアンヒドリン類を、ルテ
ニウム触媒の存在下、ヒドロペルオキシドで処理
して酸化脱水素することから成るアシルシアニド
類の新規な製造方法に関するものである。
アシルシアニド類はそれ自身殺虫、殺菌作用を
有する農薬として知られており(Ger.
Offen.1813184)、また高選択的アシル化剤として
の有用性が認められている〔D.Seebach等、
Chem.Ber.,111,2630(1978)、A.S,Howard
等、Tetrahedron Letters,1979,1339などを参
照〕。アシルシアニド類は多数の有用な複素環化
合物合成中間体として重要であり〔J.Thesing,
Angew.Chem.,68,425(1956)〕、また公知方法
によつて容易に医薬、農薬等との関連で有用なα
―ケト酸、α―アミノケトン、1,2―アミノエ
タノール誘導体、アリール酢酸誘導体等に誘導で
きる重要な一群の化合物である。
従来、このようなアシルシアニドは酸ハロゲン
化物をシアノ化することによつて製造されるが、
この場合のシアノ化方法としては、(1)化学量論量
以上の銀又は銅のシアノ化物を用いる方法、(2)ピ
リジン存在下乾燥シアン化水素を用いる方法、(3)
触媒量の銅又は亜鉛のシアン化物存在下にアルカ
リ金属シアン化物を用いる方法、(4)相間移動触媒
としてのアンモニウム塩の存在下シアン化ナトリ
ウムを用いる方法、(5)有機珪素シアン化物を用い
る方法などが知られているが、(1)〜(3)の方法は高
温かつ長時間を要するばかりでなく、しばしばい
わゆるアシルシアニドダイマーを副生し、収率が
低いという欠点を有しており、一方、(4)の方法も
30〜50%ものダイマーを副生するという難点があ
り、また(5)の方法は比較的低温かつ高収率でアシ
ルシアニドを与えるものの、シアノ化剤として用
いる有機シアノ化珪素化合物は水分に対して極め
て不安定で、水分と反応して有毒なシアン化水素
ガスを発生するため、反応系の脱水を厳密に行う
必要があり、取扱い上の困難を含む。以上のよう
な事情に鑑み、本発明者らは酸ハロゲン化物の新
規なシアノ化法を提案(特公昭57―35883、特公
昭57―77661)した。しかしながら、これら新規
シアノ化法も含め従来法では高反応性の酸ハロゲ
ン化物を出発原料とし用いるため、製造しうるア
シルシアニド類の範囲が限定される欠点を有し、
かつ一般的に酸ハロゲン化物は高価である。この
ように従来の方法は一般的かつ工業的に有利な方
法といえず、さまざまの欠点を内包するものとい
わざるを得ない。
本発明者らは、従来法に於けるかかる問題を克
服すべく鋭意研究の結果、入手容易なアルデヒド
類から簡便に製造しうるシアンヒドリン類の脱水
素反応が、ルテニウム触媒の存在下種々のヒドロ
ペルオキシド類を作用させることによつて温和な
条件下迅速に進行するという新規な事実を発見
し、これにもとづき本発明を完成させるに至つ
た。
すなわち、本発明によれば、工業的に容易に製
造されるシアンヒドリン類を原料とする効率的な
アシルシアニド類の新規製造方法が提供される。
本発明の原料であるシアンヒドリン類は前記一
般式
The present invention relates to an efficient method for producing acyl cyanides, and more particularly, to a novel method for producing acyl cyanides, which comprises treating cyanohydrin with a hydroperoxide in the presence of a ruthenium catalyst for oxidative dehydrogenation. be. Acyl cyanides themselves are known as pesticides that have insecticidal and bactericidal effects (Ger.
Offen.1813184), and its usefulness as a highly selective acylating agent [D. Seebach et al.
Chem.Ber., 111 , 2630 (1978), AS, Howard
et al., Tetrahedron Letters, 1979 , 1339]. Acyl cyanides are important as intermediates for the synthesis of many useful heterocyclic compounds [J. Thesing,
Angew .
-It is an important group of compounds that can be derived into keto acids, α-aminoketones, 1,2-aminoethanol derivatives, arylacetic acid derivatives, etc. Conventionally, such acyl cyanides are produced by cyanating acid halides, but
The cyanation methods in this case include (1) a method using a stoichiometric amount or more of silver or copper cyanide, (2) a method using dry hydrogen cyanide in the presence of pyridine, and (3) a method using dry hydrogen cyanide in the presence of pyridine.
(4) using sodium cyanide in the presence of an ammonium salt as a phase transfer catalyst; (5) using organosilicon cyanide. However, methods (1) to (3) not only require high temperatures and a long time, but also often produce so-called acyl cyanide dimers as by-products, resulting in low yields. , On the other hand, method (4) also
It has the disadvantage of producing 30 to 50% dimer as a by-product, and although the method (5) provides acyl cyanide at a relatively low temperature and high yield, the organic cyanated silicon compound used as the cyanating agent is sensitive to moisture. Because it is extremely unstable and reacts with moisture to generate toxic hydrogen cyanide gas, the reaction system must be dehydrated strictly, which poses handling difficulties. In view of the above circumstances, the present inventors proposed a new method for cyanating acid halides (Japanese Patent Publication No. 57-35883, Japanese Patent Publication No. 57-77661). However, conventional methods, including these new cyanation methods, use highly reactive acid halides as starting materials, so they have the disadvantage that the range of acyl cyanides that can be produced is limited.
Moreover, acid halides are generally expensive. As described above, the conventional method cannot be said to be a general or industrially advantageous method, and it must be said that it includes various drawbacks. As a result of intensive research in order to overcome such problems in conventional methods, the present inventors have discovered that the dehydrogenation reaction of cyanohydrins, which can be easily produced from readily available aldehydes, can be used to produce various hydroperoxides in the presence of a ruthenium catalyst. The inventors have discovered the novel fact that the process progresses rapidly under mild conditions by the action of a similar compound, and based on this discovery, they have completed the present invention. That is, according to the present invention, a novel method for efficiently producing acyl cyanides using cyanohydrins, which are easily produced industrially, as raw materials is provided. The cyanohydrins that are the raw materials of the present invention have the general formula
【式】で表わされる構造のもの、
即ち、アルデヒドシアンヒドリンであり、R1が
不飽和脂肪族系、芳香族系、複素芳香族系であれ
ばその種類を問わない。従つて、前記一般式のシ
アンヒドリン中、R3で示される有機基には、フ
エニル基、ナフチル基などのアリール基、フリル
基、チエニル基、ピロリル基、インドリル基、ピ
リジル基などの複素環基、ビニル、プロペニル。
イソプロペニル、β―スチリルなどのアルケニル
基などの有機基が包含され、反応の進行を阻害す
るものを除きあらゆる官能基が結合していても良
い。なお、上記の有機基はあくまで例示にすぎ
ず、これらに限られるものではない。これらのシ
アンヒドリン類は相当するアルデヒド類(前記シ
アンヒドリンの一般式中のR1がホルミル基に結
合した構造をもつ)から容易に得られることは広
く知られており、またこれらアルデヒド類は酸化
反応(R1―CH3→R1CHO)、gem―ジハロゲン化
物の加水分解(R1CHX2→R1CHO)ハロゲン化
物のカルボニル化(R2X→R1CHO)、Vilsmeyer
反応(R1H→R1CHO)、Gatterman―Koch反応
(R1H→RCHO)などによつて工業的に大量に製
俗することが容易である。
本反応で用いる一般式R2OOH(R2は前記と同
じである)で表わされるヒドロペルオキシドは前
記R2の範囲に属する限りいかなるものでもさし
つかえないが、化学的安定性を考慮するならば、
第2級又は第3級カルビル基でヒドロペルオキシ
ド基に結合するものが好ましく、このような有機
基R2としては、イソプロピル基、シクロヘキシ
ル基、t―ブチル基、α―テトラリル基、α―メ
チルベンジル基、α―クミル基、α―シミル基
〔o―,m―,p―;
It has a structure represented by [Formula], that is, aldehyde cyanohydrin, and the type is not limited as long as R 1 is unsaturated aliphatic, aromatic, or heteroaromatic. Therefore, in the cyanohydrin of the above general formula, the organic group represented by R 3 includes an aryl group such as a phenyl group or a naphthyl group, a heterocyclic group such as a furyl group, a thienyl group, a pyrrolyl group, an indolyl group, or a pyridyl group; vinyl, propenyl.
Organic groups such as alkenyl groups such as isopropenyl and β-styryl are included, and any functional group may be bonded except for those that inhibit the progress of the reaction. Note that the above organic groups are merely examples and are not limited thereto. It is widely known that these cyanohydrins can be easily obtained from the corresponding aldehydes (having a structure in which R 1 in the general formula of cyanohydrin is bonded to a formyl group), and these aldehydes can also be obtained by oxidation reaction ( R 1 - CH 3 → R 1 CHO), hydrolysis of gem-dihalides (R 1 CHX 2 → R 1 CHO), carbonylation of halides (R 2 X → R 1 CHO), Vilsmeyer
It is easy to produce industrially in large quantities by reaction (R 1 H→R 1 CHO), Gatterman-Koch reaction (R 1 H→RCHO), etc. The hydroperoxide represented by the general formula R 2 OOH (R 2 is the same as above) used in this reaction may be any one as long as it falls within the range of R 2 above, but considering chemical stability,
A secondary or tertiary carbyl group that is bonded to the hydroperoxide group is preferable, and examples of such organic group R2 include isopropyl group, cyclohexyl group, t-butyl group, α-tetralyl group, α-methylbenzyl group. group, α-cumyl group, α-simyl group [o-, m-, p-;
【式】〕、p―フエニレン
ジイソプロピル基
[Formula]], p-phenylene diisopropyl group
【式】などが例示
される。
本反応は、ルテニウム触媒の存在下に実施され
るが、このルテニウム触媒としては、ルテニウム
の原子価が零価〜3価のあらゆるルテニウム金属
又は化合物を用いることが出来る。この場合のル
テニウム金属又は化合物は公知方法で不活性な担
体、例えば、アルミナ、シリカゲル、活性炭など
に担持して用いることも可能である。本反応に用
いるルテニウム化合物を例示すると、金属ルテニ
ウム粉末、コロイド状ルテニウム、活性炭担持ル
テニウム、ルテニウムカルボニル、(1,3,5
―シクロオクタトリエン)(1,5―シクロオク
タジエン)ルテニウム、ルテニウムジクロリド、
ルテニウムジブロミド、酸化ルテニウム、ルテニ
ウムアセチルアセトナート、ルテニウムトリクロ
リド、ルテニウムトリブロミド、ルテニウムトリ
ヨージド、ジクロロトリカルボニルルテニウムダ
イマー、ジクロロ―π―ベンゼンルテニウム・
DMSO付加物、トリストリフエニルホスフイン
ルテニウムジクロリド、トリストリフエニルホス
フインルテニウムジブロミド、クロロヒドリドト
リストリフエニルホスフインルテニウム、ブロモ
ヒドリドトリストリフエニルホスフインルテニウ
ム、トリストリ(p―クロロフエニル)ホスフイ
ンルテニウムジクロリド、トリストリフエニルホ
スフインルテニウムヒドリドアセタート、トリス
トリフエニルホスフインルテニウムヒドリドビバ
ロアート、トリストリフエニルホスフインクロロ
ジフエニルシリルルテニウムヒドリド等を挙げる
ことができる。なお、これらルテニウム触媒の使
用量はいわゆる触媒量で充分であり、シアンヒド
リンの構造によつてはその1/1000モル比程度の
量であつても室温に於て充分迅速にアシルシアニ
ド類を得ることが出来る。
本反応は無溶媒でも進行するが、不活性な溶媒
中で実施することも可能である。このような溶媒
を例示すると、ベンゼン、トルエン、アセトン、
ジクロルメタン、ヘキサン、水、酢酸、酢酸エチ
ル、アセトニトリル、t―ブチルアルコール.ク
ロルベンゼン、エーテル、テトラヒドロフラン、
スルホランなど通常用いられる溶媒類が挙げられ
る。
本発明の反応は多くの場合室温でも迅速に進行
し、またシアンヒドリンの構造によつては発熱を
除去するため冷却を要する場合もあるが、反応速
度が低い場合には加熱下に実施することも出来、
通常−20℃〜+100℃、好ましくは0℃〜80℃の
温度範囲で実施される。
シアンヒドリンとヒドロペルオキシドの量関係
は、いずれが過剰であつても反応は進行するが、
通常、シアンヒドリン/ヒドロペルオキシドのモ
ル比で0.1〜2の範囲で実施され、好ましくは0.2
〜1の範囲である。
生成物の分離は、反応混合物を必要に応じ、実
質的に水に不溶の溶剤を加え、不溶性触媒の場合
には、濾過、遠心分離等により不溶物を分離回収
の後、水(必要に応じ環元剤を含んでいてもよ
い)で洗い、有機層を必要に応じて溶媒をストリ
ツプした後、蒸留、クロマトグラフイー又は再結
晶など通常の分離操作によつて容易に行うことが
出来る。
以上のように本発明によれば、入手容易な広い
範囲のシアンヒドリン類を原料に用いて、不飽和
脂肪族、芳香族、複素環族を問わず、巾広いアシ
ルシアニド類を、穏和な条件下、好収率に得るこ
とが出来る。た反応操作、生成物の分離にも煩雑
な操作を必要とせず、所望のアシルシアニドを簡
単に得ることが出来、工業的見地から極めて有利
な方法ということが出来る。
次に実施例に基づき更に詳細に説明する。
実施例 1
窒素雰囲気下でジクロロトリストリフエニルホ
スフインルテニウム48mg(5×10-2mmol)及びマ
ンデロニトリル0.59ml(5mmol)をベンゼン5ml
に溶解し、室温に於て撹拌しつつt―ブチルヒド
ロペルオキシドの水溶液(70%)1.28ml(10mm
ol)を10分間かけて滴下し、その後50分撹拌を続
けた。ジフエニルエーテル391mgを内部標準物と
して加え、ガスクロマトグラフイーにより分析し
た結果、ベンゾイルシアニドが92.9%の収率で生
成していた。
全く同様の反応を繰返し、ジフエニルエーテル
を加えずに反応溶液をエーテル20mlに加え、水5
mlで2回洗い、硫酸マグネシウムで乾燥、次いで
濾過し濾液から溶剤をロータリーエバポレーター
で留去し、残つた油状物をシリカゲルクロマトグ
ラフイー(展開溶剤:ヘキサン―ベンゼン、グラ
デイエント)で精製し、塩化メチレン―ペンタン
の混合溶媒から再結晶の結果、mp32.4〜33.2℃を
示す純粋なベンゾイルシアニドを得た。
実施例 2〜11
実施例1と全く同様の方法で他のシアンヒドリ
ン類の反応を行つた結果を表―1にまてめて示し
た。収率は特記しない限りガスクロマトグラフイ
ーによつて求めた。なお、表―1には実施例1の
結果も含めて示してある。Examples include [Formula]. This reaction is carried out in the presence of a ruthenium catalyst, and any ruthenium metal or compound in which the valence of ruthenium is zero to trivalent can be used as the ruthenium catalyst. In this case, the ruthenium metal or compound can be supported on an inert carrier such as alumina, silica gel, activated carbon, etc. by a known method. Examples of ruthenium compounds used in this reaction include metal ruthenium powder, colloidal ruthenium, activated carbon-supported ruthenium, ruthenium carbonyl, (1,3,5
-cyclooctatriene)(1,5-cyclooctadiene)ruthenium, ruthenium dichloride,
Ruthenium dibromide, ruthenium oxide, ruthenium acetylacetonate, ruthenium trichloride, ruthenium tribromide, ruthenium triiodide, dichlorotricarbonyl ruthenium dimer, dichloro-π-benzene ruthenium
DMSO adduct, tristriphenylphosphine ruthenium dichloride, tristriphenylphosphine ruthenium dibromide, chlorohydrido tristriphenylphosphine ruthenium, bromohydrido tristriphenylphosphine ruthenium, tristri(p-chlorophenyl)phosphine ruthenium dichloride, Examples include tristriphenylphosphine ruthenium hydride acetate, tristriphenylphosphine ruthenium hydrido bivaroate, tristriphenylphosphine chlorodiphenylsilylruthenium hydride, and the like. Note that the amount of these ruthenium catalysts used is a so-called catalytic amount, and depending on the structure of cyanohydrin, it is possible to obtain acyl cyanides sufficiently quickly at room temperature even with an amount of about 1/1000 molar ratio. I can do it. Although this reaction proceeds without a solvent, it can also be carried out in an inert solvent. Examples of such solvents include benzene, toluene, acetone,
Dichloromethane, hexane, water, acetic acid, ethyl acetate, acetonitrile, t-butyl alcohol. Chlorbenzene, ether, tetrahydrofuran,
Examples include commonly used solvents such as sulfolane. The reaction of the present invention often proceeds rapidly even at room temperature, and depending on the structure of the cyanohydrin, cooling may be required to remove heat generation, but if the reaction rate is slow, it may be carried out under heating. Done,
It is usually carried out at a temperature range of -20°C to +100°C, preferably 0°C to 80°C. The relationship between the amounts of cyanohydrin and hydroperoxide is such that the reaction will proceed even if either is in excess.
Usually carried out at a molar ratio of cyanohydrin/hydroperoxide in the range of 0.1 to 2, preferably 0.2.
~1. To separate the product, add a solvent that is substantially insoluble in water to the reaction mixture as necessary, and in the case of an insoluble catalyst, remove the insoluble matter by filtration, centrifugation, etc., and then add water (if necessary). After washing the organic layer with a solvent (which may contain a reducing agent) and stripping the organic layer of the solvent if necessary, the separation can be easily carried out by conventional separation operations such as distillation, chromatography, or recrystallization. As described above, according to the present invention, a wide range of acyl cyanides, regardless of whether they are unsaturated aliphatic, aromatic, or heterocyclic, can be produced under mild conditions by using a wide range of easily available cyanohydrins as raw materials. It can be obtained in good yield. The desired acyl cyanide can be easily obtained without requiring complicated reaction operations or product separation, and can be said to be an extremely advantageous method from an industrial standpoint. Next, a more detailed explanation will be given based on examples. Example 1 48 mg (5 x 10 -2 mmol) of dichlorotritriphenylphosphineruthenium and 0.59 ml (5 mmol) of mandelonitrile were added to 5 ml of benzene under a nitrogen atmosphere.
of t-butyl hydroperoxide (70%) and stirred at room temperature.
ol) was added dropwise over 10 minutes, and stirring was continued for 50 minutes. 391 mg of diphenyl ether was added as an internal standard, and analysis by gas chromatography revealed that benzoyl cyanide was produced in a yield of 92.9%. Repeat the exact same reaction, add the reaction solution to 20 ml of ether without adding diphenyl ether, and add 5 ml of water.
ml twice, dried over magnesium sulfate, filtered, and distilled the solvent from the filtrate using a rotary evaporator. The remaining oil was purified by silica gel chromatography (developing solvent: hexane-benzene, gradient) and purified with methylene chloride. - As a result of recrystallization from a mixed solvent of pentane, pure benzoyl cyanide with a mp of 32.4-33.2℃ was obtained. Examples 2 to 11 Table 1 shows the results of reactions of other cyanohydrins in exactly the same manner as in Example 1. Yields were determined by gas chromatography unless otherwise specified. Note that Table 1 also shows the results of Example 1.
【表】【table】
【表】
*( )内は単離収率を示す。
[Table] *The numbers in parentheses indicate the isolated yield.
Claims (1)
れる有機基を示す)で表わされるシアンヒドリン
類を、ルテニウム触媒の存在下、一般式R2OOH
(式中R2はアルキル基、シクロアルキル基及びア
ラルキル基の中から選ばれる有機基を示す)で表
わされるヒドロペルオキシドと反応させることを
特徴とする、一般式R1COCN(式中、R1は前記と
同じである)で表わされるアシルシアニド類を製
造する方法。[Claims] 1. A cyanohydrin represented by the general formula [Formula] (wherein R 1 represents an organic group selected from an aryl group, an alkenyl group, and a heterocyclic group) in the presence of a ruthenium catalyst. Below, general formula R 2 OOH
(In the formula, R 2 represents an organic group selected from an alkyl group, a cycloalkyl group, and an aralkyl group ) . is the same as above).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59040184A JPS60184056A (en) | 1984-03-01 | 1984-03-01 | Preparation of acyl cyanide |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59040184A JPS60184056A (en) | 1984-03-01 | 1984-03-01 | Preparation of acyl cyanide |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60184056A JPS60184056A (en) | 1985-09-19 |
JPH0140024B2 true JPH0140024B2 (en) | 1989-08-24 |
Family
ID=12573694
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP59040184A Granted JPS60184056A (en) | 1984-03-01 | 1984-03-01 | Preparation of acyl cyanide |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60184056A (en) |
-
1984
- 1984-03-01 JP JP59040184A patent/JPS60184056A/en active Granted
Also Published As
Publication number | Publication date |
---|---|
JPS60184056A (en) | 1985-09-19 |
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