JPS6377834A - Production of methyl ketones - Google Patents
Production of methyl ketonesInfo
- Publication number
- JPS6377834A JPS6377834A JP21805986A JP21805986A JPS6377834A JP S6377834 A JPS6377834 A JP S6377834A JP 21805986 A JP21805986 A JP 21805986A JP 21805986 A JP21805986 A JP 21805986A JP S6377834 A JPS6377834 A JP S6377834A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- formula
- acetylene
- reaction
- group
- 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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical class CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 42
- -1 aryl telluric acid Chemical compound 0.000 claims abstract description 35
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000001424 substituent group Chemical group 0.000 claims abstract description 9
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 3
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 12
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract description 27
- 238000006243 chemical reaction Methods 0.000 abstract description 19
- 239000002904 solvent Substances 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 2
- 229920001197 polyacetylene Polymers 0.000 abstract description 2
- JPIIVHIVGGOMMV-UHFFFAOYSA-N ditellurium Chemical compound [Te]=[Te] JPIIVHIVGGOMMV-UHFFFAOYSA-N 0.000 abstract 1
- 150000004820 halides Chemical class 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 150000007524 organic acids Chemical class 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 238000007259 addition reaction Methods 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OFDISMSWWNOGFW-UHFFFAOYSA-N 1-(4-ethoxy-3-fluorophenyl)ethanamine Chemical compound CCOC1=CC=C(C(C)N)C=C1F OFDISMSWWNOGFW-UHFFFAOYSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-UHFFFAOYSA-N 13-cis retinol Natural products OCC=C(C)C=CC=C(C)C=CC1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- FPIPGXGPPPQFEQ-BOOMUCAASA-N Vitamin A Natural products OC/C=C(/C)\C=C\C=C(\C)/C=C/C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-BOOMUCAASA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- LLCSWKVOHICRDD-UHFFFAOYSA-N buta-1,3-diyne Chemical group C#CC#C LLCSWKVOHICRDD-UHFFFAOYSA-N 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004653 carbonic acids Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229940074994 mercuric sulfate Drugs 0.000 description 1
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 150000003556 thioamides Chemical class 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 235000019155 vitamin A Nutrition 0.000 description 1
- 239000011719 vitamin A Substances 0.000 description 1
- 229940045997 vitamin a Drugs 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野]
本発明は、末端アセチレン化合を有する化合物から対応
するメチルケトンを製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a corresponding methyl ketone from a compound having a terminal acetylene compound.
アセチレンに対する水の付加反応はアセトアルデヒドの
合成法として利用され、この反応に用いる触媒は種々提
案されている。その主なものとしてはルイス酸系のもの
、または硫酸第二水銀などHg(U )塩を用いる方法
が知られている。The addition reaction of water to acetylene is used as a method for synthesizing acetaldehyde, and various catalysts have been proposed for use in this reaction. The main known methods include methods using Lewis acids or Hg(U) salts such as mercuric sulfate.
一方、アリールチルリン酸無水物を用いて不飽和化合物
を酸化する例として、硫酸共存下で下記の如くオレフィ
ンをジアセトキシ化する例が報告0
0Ac OAc〔日本化学会主催、第
13回有機硫黄・リン化合物討論会(1985年17J
’)、講演要旨集p、57.園田ら〕アセチレン化合物
に対する=、(みは、未だ見られない。On the other hand, as an example of oxidizing an unsaturated compound using an aryl phosphoric anhydride, there is a reported example of diacetoxylating an olefin in the presence of sulfuric acid as shown below.
0Ac OAc [The 13th Symposium on Organic Sulfur and Phosphorus Compounds, sponsored by the Chemical Society of Japan (1985 17J
'), collection of lecture abstracts p, 57. [Sonoda et al.] =, (for acetylene compounds) has not yet been seen.
酸触媒は反応性が低く実用的でない。 Acid catalysts have low reactivity and are not practical.
また、)Ig(II)塩を用いる方法はHg(IT)の
毒性が高いため実用面で取扱い上の問題が多いことと、
且つ、反応の選択性が低く、末端アセチレン結合と内部
アセチレン結合とを区別して水を付加することが困難で
あるという難点がある。In addition, the method using )Ig(II) salt has many practical handling problems due to the high toxicity of Hg(IT).
In addition, the selectivity of the reaction is low, and it is difficult to distinguish between terminal acetylene bonds and internal acetylene bonds when adding water.
本発明者らは、末端アセチレン結合を有する化合物に水
を付加させるにあたり、アリールチルリン酸無水物を存
在させることによって、意外にもア・ごチレン化合物の
内部アセチレン結合を保持したまま、末端アセチレン結
合のみに選択的に水を付加して対応するメチルケトンを
得ることができることを見出し本発明を完成した。When adding water to a compound having a terminal acetylene bond, the present inventors unexpectedly discovered that by adding water to a compound having a terminal acetylene bond, by adding an arylthyl phosphoric acid anhydride, the terminal acetylene bond was The present invention was completed by discovering that the corresponding methyl ketone can be obtained by selectively adding water only to the bond.
本発明は、「末端アセチレン結合を有する化合物に水を
付加してメチルケトン類を製造するにあたり、下記一般
式で表されるアリールチルリン酸無水物の存在下でプロ
トンを供給し得る化合物と該アセチレン化合物とを反応
させることを特徴とするメチルケトン類の製造方法。The present invention relates to a compound capable of supplying protons in the presence of an aryl phosphoric acid anhydride represented by the following general formula and the acetylene bond in the production of methyl ketones by adding water to a compound having a terminal acetylene bond. A method for producing methyl ketones, the method comprising reacting them with a compound.
を要旨とする。The gist is:
本発明の方法は、モノアセチレン、ジアセチレン1 ま
たはポリアセチレンで末端アセチレン結合を有する多く
のアセチレン化合物に適用することができる。The method of the invention can be applied to many acetylene compounds having terminal acetylene bonds in monoacetylene, diacetylene 1 or polyacetylene.
また、チオール、チオアミド、チオエステル。Also thiols, thioamides, thioesters.
ホスフィン、ホスファイトなどの特に酸化され易い基を
除く種々の置換基を有するアセチレン化合物にも適用す
ることができ、その末端アセチレン結合に選択的に水を
付加することができる。It can also be applied to acetylene compounds having various substituents other than groups that are particularly easily oxidized such as phosphine and phosphite, and water can be selectively added to the terminal acetylene bonds.
本発明の方法によって次式fatまたは[blに示され
るような末端アセチレン結合を有する化合物に水を付加
して対応するメチルケトンを得ることができるが、本発
明の方法は特に、弐(C1に示されるような化合物に適
用したとき、その内部アセチレン結合を保持したまま、
末端アセチレン結合のみに選択的に水を付加して対応す
るメチルケトンを得ることかできるという特徴を有する
。Although the method of the present invention allows water to be added to a compound having a terminal acetylene bond as shown in the following formula fat or [bl, the corresponding methyl ketone can be obtained. When applied to a compound that retains its internal acetylene bond,
It has the characteristic that water can be selectively added only to the terminal acetylene bond to obtain the corresponding methyl ketone.
−一→ CL C−(RJ、1− CCH3(CI
R’−CミC−(R2)、1− CCH:+(式中、
R’は水素原子、飽和または不飽和の脂肪族化合物、脂
環式化合物、ヒドロ芳香族化合物。-1 → CL C-(RJ, 1-CCH3(CI R'-CmiC-(R2), 1-CCH:+(in the formula,
R' is a hydrogen atom, a saturated or unsaturated aliphatic compound, an alicyclic compound, or a hydroaromatic compound.
あるいは芳香族化合物などに属する各種炭化水素の一価
の原子団を、R2は炭素数1個以上の二価の炭化水素基
でnはOまたは1を、またR3は飽和または不飽和の脂
肪族化合物、脂Iス弐化合物、ヒドロ万香族化合物、あ
るいは芳香族化合物などに属する各種炭化水素の一価の
原子団を表す、)本発明において用いられるアリールチ
ルリン酸は下記一般式で表される。Alternatively, monovalent atomic groups of various hydrocarbons belonging to aromatic compounds, etc., R2 is a divalent hydrocarbon group having 1 or more carbon atoms, n is O or 1, and R3 is a saturated or unsaturated aliphatic group. The aryl phosphoric acid used in the present invention is represented by the following general formula. Ru.
Ar−は了り−ル2+(を表し、アリール基がフェニル
8ナフチル、アントリル、フェナントリルなどの無置換
体のほか、各種の置換基を有するこれらの置換体、ある
いは更に複数の置換基を有する多置換体であるアリール
チルリン酸無水物を用いることができる。アリール基の
置換基としては、炭素数1〜8のアルキル些またはアル
コキシル基。Ar- represents an aryl group (2+), in which the aryl group is phenyl, 8, unsubstituted such as naphthyl, anthryl, phenanthryl, these substituted products with various substituents, or polyesters with multiple substituents. A substituted aryl phosphoric acid anhydride can be used.As a substituent for the aryl group, an alkyl group having 1 to 8 carbon atoms or an alkoxyl group can be used.
置換または無置換フェノキシ店、置換または無置換アミ
ノ基、ベンジル基、ハロゲン原子を挙げることができる
。好ましくは、アリール基の71 iD基としてメトキ
シ基、エトキシ基、ブトキシ基、フェノキシ凸などの電
子供与性の基を有するヘンインテルリン酸。無水物また
はナックレンチルリン酸無水物である。Examples include substituted or unsubstituted phenoxy groups, substituted or unsubstituted amino groups, benzyl groups, and halogen atoms. Preferably, heminterlic acid has an electron-donating group such as a methoxy group, an ethoxy group, a butoxy group, or a convex phenoxy group as the 71 iD group of the aryl group. anhydride or nuclentil phosphate anhydride.
アセチレン化合物に対するアリールチルリン酸無水物の
使用量比は1〜20モル%の範囲がよく、好ましくは5
〜15モル%、更に好ましくは8〜12モル%の範囲で
ある。1モル%未満では反応の所要時間が多くて実用的
でなく、また20モル%を超えて用いても効果の増加は
JT!\5ろれない。The ratio of the aryl phosphoric acid anhydride to the acetylene compound is preferably in the range of 1 to 20 mol%, preferably 5.
The range is from 15 mol% to 15 mol%, more preferably from 8 to 12 mol%. If it is less than 1 mol%, the reaction time will be long and it is not practical, and even if it is used in excess of 20 mol%, the effect will not increase. \5 I can't laugh.
本発明の方法において用いられるプロトンを供給し得る
化合物としては、水のほか、炭酸など無機の弱酸、カル
ボン欣、有機スルホン酸、有機ホスホン酸などの有NH
を挙げることができ、これらのプロトンを供給し得る化
合物は原料アセチレン化合物の末0ぜ、;アセチレン結
合1個に対して1モル)!以上、好ましくは2モル量以
上を用いろ。Compounds capable of supplying protons used in the method of the present invention include, in addition to water, inorganic weak acids such as carbonic acid, NH-containing acids such as carbonic acids, organic sulfonic acids, and organic phosphonic acids.
The compounds that can supply these protons are the end of the starting acetylene compound (1 mole per acetylene bond)! As mentioned above, preferably use an amount of 2 moles or more.
カルボン酸としては、脂肪族または芳香族のモノカルボ
ン酸類、ジカルボン酸類、ポリカルボン酸類が用いられ
る。好ましくは常温で液体である炭素数2〜9の、更に
好ましくは水との混合性のよい炭素数2〜3の直鎖脂肪
族飽和モノカルボン酸類が用いられる。As the carboxylic acid, aliphatic or aromatic monocarboxylic acids, dicarboxylic acids, and polycarboxylic acids are used. Preferably, straight-chain aliphatic saturated monocarboxylic acids having 2 to 9 carbon atoms, which are liquid at room temperature, and more preferably 2 to 3 carbon atoms, are used, which have good miscibility with water.
本発明の方法においては、反応に際して反応溶媒を使用
するのが好ましい。反応溶媒としては、反応を阻害する
ものは避けねばならないが、反応混合物をよく溶解する
ものが有Fllであり比較的極性の高い溶媒が好ましい
。In the method of the present invention, it is preferable to use a reaction solvent during the reaction. As the reaction solvent, it is necessary to avoid those that inhibit the reaction, but it is preferable to use a solvent that dissolves the reaction mixture well and has relatively high polarity.
使用される溶媒の具体例としては、酢酸、プロピオン酸
などカルボン酸類及びその無水物、ツタノール1 エタ
ノール、プロパツール、ブタノールなどアルコール類、
\3N−ジメチルホルムアミド。Specific examples of solvents used include carboxylic acids and their anhydrides such as acetic acid and propionic acid, alcohols such as tutanol, ethanol, propatool, and butanol;
\3N-dimethylformamide.
N、N−ジメチルアセトアミドなどアミド類、アセトニ
トリル、イソブチロニトリルなどニトリル類、エチレン
グリコールジメチルエーテル、テトラハイドロフラン、
ジオキサン、セロソルブなどエーテル類、その他炭酸エ
ステル+1、δ−ブチロラクトン、塩化メチレン、スル
ホラン、ツメチルスルホキシド、ピリジン、モルホリン
などを挙げることができる。Amides such as N,N-dimethylacetamide, nitriles such as acetonitrile and isobutyronitrile, ethylene glycol dimethyl ether, tetrahydrofuran,
Examples include ethers such as dioxane and cellosolve, carbonate ester +1, δ-butyrolactone, methylene chloride, sulfolane, trimethylsulfoxide, pyridine, and morpholine.
酢酸は、反応溶媒の機能を有するとともにプロトンを供
給することができ、原料アセチレン化合物の末端アセチ
レン結合1個に対して1モル星以上を用いると水を供給
することなしにアセチレン化合物への水の付加反応を進
めることができるので特に好ましい。Acetic acid has the function of a reaction solvent and can supply protons, and if 1 mol or more of acetic acid is used per terminal acetylene bond of the raw acetylene compound, water can be added to the acetylene compound without supplying water. This is particularly preferred since it allows the addition reaction to proceed.
反応温度は、室温以上、好ましくは50〜150℃の範
囲が実用上有利である。また、低沸点の原料および/ま
たは溶媒を使用する場合は、加圧下で行うこともできる
。反応の雰囲気としては大気圧下でよいが、窒素雰囲気
で行ってもよい。It is practically advantageous for the reaction temperature to be at least room temperature, preferably in the range of 50 to 150°C. Moreover, when using a raw material and/or a solvent with a low boiling point, it can also be carried out under pressure. The reaction atmosphere may be atmospheric pressure, but may also be carried out in a nitrogen atmosphere.
反応後は、常法に従って蒸留、再結晶等により生成物を
分離精製すればよい。After the reaction, the product may be separated and purified by distillation, recrystallization, etc. in accordance with conventional methods.
アリールチルリン酸無水物は、弐fi+に示すように各
種の芳香族炭化水素(ArHと記す)とTe”のノ\ロ
ゲン化物とから合成することができる。Arylthyl phosphoric acid anhydride can be synthesized from various aromatic hydrocarbons (denoted as ArH) and halogenated Te'' as shown in 2fi+.
また、アリールチルリン酸無水物は反応の過程でジアリ
ールジチルリドに変化し、反応後に回収することができ
る。回収されたジアリールジチルリドより式(2)の如
くして容易にアリールチルリン酸無水物が得ろ羽、再使
用することができる。Furthermore, arylthylphosphoric anhydride changes into diaryldityllide during the reaction process, and can be recovered after the reaction. An aryl phosphoric acid anhydride can be easily obtained from the recovered diaryl dityllide as shown in formula (2) and can be reused.
アリールチルリン酸無水物の実消費量は操作上のロス分
のみであり、これに対応する分の補給を行えばよく費用
を軽減することができる。The actual amount of aryl phosphoric acid anhydride consumed is only the operational loss, and costs can be reduced by replenishing the amount corresponding to this.
また、使用に際してCu(H)、 Fe(r!J)また
はキノン類などの酸化剤を共存させ机ば、アリールチル
リン酸無水物の系内での再生により連VC使用も可能と
なる。Furthermore, if an oxidizing agent such as Cu(H), Fe(r!J) or quinones is co-present during use, continuous VC use becomes possible by regenerating the arylthyl phosphoric anhydride within the system.
本技術の応用性は極めて高く、ステロイド系化合物の側
鎖の化学修飾、ビタミンA合成用中間体の合成、またプ
ロスタグランジン系化合物の中181体の合成、或いは
天然ポリイン系化合物の合成など各種の反応への適用な
ど種々の用途への利用が考えられる。The applicability of this technology is extremely high, and it can be used for various purposes such as chemical modification of side chains of steroid compounds, synthesis of intermediates for vitamin A synthesis, synthesis of 181 of prostaglandin compounds, and synthesis of natural polyyne compounds. It can be used for various purposes such as application to the reaction of
〔発明の効果]
本発明によって得られる効果は;
1) アセチレン化合物の末端アセチレン粘合のみに選
択的に水を付加することができる。[Effects of the Invention] The effects obtained by the present invention are: 1) Water can be selectively added only to the terminal acetylene viscosity of an acetylene compound.
2) アリールチルリン酸無水物は作用が穏やかである
ため、種々の置換基を有するアセチレン化合物に適用す
ることができ、それらの置換基に変化を与えろことなく
末端アセチレン結合のみにaUR的に水を付加すること
ができる。2) Arylthyl phosphoric acid anhydride has a mild action, so it can be applied to acetylene compounds with various substituents, and it can be used to add water to only the terminal acetylene bond in terms of aUR without changing the substituents. can be added.
3) アリールチルリン酸無水物は、少量の添加で反応
を著しく促進する効果を発揮するので力旦媒發の1吏用
でよい。3) Arylthyl phosphoric acid anhydride exhibits the effect of significantly accelerating the reaction even when added in a small amount, so it may be sufficient to use just one portion of the dynamo.
4) アリールチルリン酸無水物は、Hg(II)のよ
うな毒性を有さないため扱い易い。4) Arylthyl phosphate anhydride is easy to handle because it does not have toxicity like Hg(II).
以下、参考例、実施例および比較例により未発明を具体
的に説明する。Hereinafter, the uninvention will be specifically explained using reference examples, working examples, and comparative examples.
(参考例)アリールチルリン酸無水物の合成;l)ρ−
メトキシベンゼンチルリン酸無水物の合成;(i)p−
メトキシフェニルテルルトリクロリドの合成;
四塩化テルル12 g (0,0445モル)とアニソ
ール14.4 g (0,133モル)とを無水クロロ
ホルム75−に加え、湿気を避けて還流下に2時間加熱
した。(Reference example) Synthesis of aryl phosphoric acid anhydride; l) ρ-
Synthesis of methoxybenzenethyl phosphoric anhydride; (i) p-
Synthesis of methoxyphenyltellurium trichloride; 12 g (0,0445 mol) of tellurium tetrachloride and 14.4 g (0,133 mol) of anisole were added to anhydrous chloroform 75- and heated under reflux for 2 hours while avoiding moisture. did.
反応混合物は反応の過程でいったん溶解し、更に反応が
進むにつれて黄色固体が析出した。The reaction mixture once dissolved during the course of the reaction, and as the reaction progressed further, a yellow solid precipitated.
反応終了後、室温で1時間放冷し、析出物をろ別して少
量のクロロホルムで洗浄した後、減圧下で乾燥した。
融点:190〜192℃の黄色葉状結晶12.8gが得
られた。(収率:88%)。After the reaction was completed, the mixture was allowed to cool at room temperature for 1 hour, and the precipitate was filtered off, washed with a small amount of chloroform, and then dried under reduced pressure.
12.8 g of yellow foliate crystals with a melting point of 190-192°C were obtained. (Yield: 88%).
プロトンNMRおよびIR分析によって、生成物は標記
のp−メトキシフェニルテルルトリクロリドと同定され
た。Proton NMR and IR analysis identified the product as the title p-methoxyphenyltellurium trichloride.
(ii) P−メトキシベンゼンチルリン酸無水物の
合成;
炭酸ナトリウム10%水溶液100−に上記(i)で得
た化合物5gを加え、室温で30分間攪拌した後、酢酸
20%水溶液で中和した。−夜静″f11々、析出した
結晶をろ別し、減圧下60℃で乾燥した。(ii) Synthesis of P-methoxybenzenethyl phosphoric anhydride; Add 5 g of the compound obtained in (i) above to 10% aqueous sodium carbonate solution, stir at room temperature for 30 minutes, and then neutralize with 20% acetic acid aqueous solution. did. - At night, the precipitated crystals were filtered off and dried at 60°C under reduced pressure.
収率は定量的であった。(融点=205〜210℃)。The yield was quantitative. (Melting point = 205-210°C).
2) 上記の方法に準じて、第1表に示す各種のアリー
ルチルリン酸無水物を合成した。2) According to the above method, various aryl phosphoric acid anhydrides shown in Table 1 were synthesized.
実施例−1゜
フェニルアセチレンよりアセトフェノンの合成;フェニ
ルアセチレン0.153g (1,5mmol)とρ−
メトキシベンゼンチルリン酸無水物0.08g(0,1
5mmol)とを酢酸41R1に加え、攪拌しながら加
熱し還流下で20時間反応させた。Example-1゜Synthesis of acetophenone from phenylacetylene; 0.153 g (1.5 mmol) of phenylacetylene and ρ-
Methoxybenzenethyl phosphoric anhydride 0.08g (0,1
5 mmol) was added to acetic acid 41R1, heated with stirring, and reacted under reflux for 20 hours.
反応後、減圧下で酢酸を留去し、次いでエーテル10−
を加えて得られたエーテル溶液を炭酸水素ナトリウム5
%水溶液で洗浄し、無水硫酸マグネシウムで乾燥した。After the reaction, acetic acid was distilled off under reduced pressure, and then ether 10-
The ether solution obtained by adding
% aqueous solution and dried over anhydrous magnesium sulfate.
次いで減圧下でエーテル溶液よりエーテルを留去し、残
渣をベンゼン−ヘキサン(2:l)混合物を溶媒として
シリカゲルのカラムクロマトグラフィで予備的精製を行
ない、続いてクロロホルムを溶媒としてゲル浸透型(G
PC)クロマトグラフ(日本分析工業(掬製、LC−0
9型、JAIGEL−1)1および一2]1カラム)に
より分離精製して反応生成物を菫AMし、アセトフェノ
ンO,161gを得た。(収率:89%)。Next, ether was distilled off from the ether solution under reduced pressure, and the residue was preliminarily purified by silica gel column chromatography using a benzene-hexane (2:l) mixture as a solvent, followed by gel permeation (G) column chromatography using chloroform as a solvent.
PC) Chromatograph (Japan Analysis Industry Co., Ltd., manufactured by Kiki, LC-0
9 type, JAIGEL-1) 1 and 2] column), the reaction product was purified by Sumitomo AM to obtain 161 g of acetophenone O. (Yield: 89%).
実施例−2〜6゜
実施例−1に準じ、ρ−メトキシヘンゼンテルリン酸の
代りに各種のアリールチルリン酸無水物を用いて反応を
行った結果を第1表に示す。Examples 2 to 6 According to Example 1, reactions were carried out using various aryl phosphoric anhydrides instead of ρ-methoxyhensentelluric acid. The results are shown in Table 1.
実施例−7〜11.および比較例−1〜3゜実施例−1
に準じ、p−メトキシベンゼンチルリン酸を用いて各種
のアセチレン化合物について反応を試みた結果を第2表
に示す。Examples-7 to 11. and Comparative Examples-1 to 3゜Example-1
Table 2 shows the results of attempts to react various acetylene compounds using p-methoxybenzenethyl phosphoric acid according to the above.
各実施例に示されるように、アセチレン化合物の末端ア
セチレン結合に水が付加して対応するメチルケトンが得
られる。また、内部アセチレン結合を有するアセチレン
化合物の場合には、その内部アセチレン結合を保持した
まま、末端アセチレン結合のみに選択的に水が付加して
対応するメチルケトンが得られる。As shown in each example, water is added to the terminal acetylene bond of an acetylene compound to yield the corresponding methyl ketone. Further, in the case of an acetylene compound having an internal acetylene bond, water is selectively added only to the terminal acetylene bond while retaining the internal acetylene bond to obtain the corresponding methyl ketone.
一方、比較例に示されるように、分子内に内部アセチレ
ン結合のみで末端アセチレン結合を有さないアセチレン
化合物の場合には水の付加反応が起こらず、原料アセチ
レン化合物はそのまま回収された。On the other hand, as shown in the comparative example, in the case of an acetylene compound having only internal acetylene bonds and no terminal acetylene bonds in the molecule, no water addition reaction occurred, and the raw acetylene compound was recovered as it was.
第1表 反応条件;溶媒:酢酸、還流下720
時間。Table 1 Reaction conditions; Solvent: Acetic acid, 720 ml under reflux
time.
第2表 反応条件;溶媒;酢酸、還流
下720時間。Table 2 Reaction conditions: Solvent: Acetic acid, 720 hours under reflux.
特許出願人 日東化学工業科式会社
子 続 補 正 書 (自発)昭和62年8月
25日
特許庁長官 小 川 邦 夫 殿
1、$件の表示
昭和61年特許願第218059号
2、 発明の名称
メチルケトン類の製造方法
3、 補正をする者
事件との関係 特許出願人
〒100東京都千代田区丸の内−丁目5番1号4、 補
正により増加する発明の数
つ
6、 補正の内容
(1) 明細書の口発明の詳キ[1な説明−・のqに
ついて次のとおりに補正する。Patent Applicant Nitto Chemical Industry Co., Ltd. Subsidiary Amendment (Spontaneous) August 25, 1988 Director General of the Patent Office Kunio Ogawa 1, Indication of $ 1986 Patent Application No. 218059 2, Invention Name Process for producing methyl ketones 3 Relationship with the case of the person making the amendment Patent applicant 5-1-5 Marunouchi, Chiyoda-ku, Tokyo 100 4 Number of inventions increased by the amendment 6 Contents of the amendment (1) Regarding q in the description of the invention in the description, q is amended as follows.
1) 第13頁、下から第3マラ〜第2行、「p−メト
キシベンゼンチルリン酸」を7p−メトキシベンゼンチ
ルリン酸無水物」に訂正する。1) On page 13, 3rd column to 2nd line from the bottom, "p-methoxybenzenethyl phosphoric acid" is corrected to "7p-methoxybenzenethyl phosphoric anhydride".
2) 第14頁、第2行〜第3行、「p−メトキシヘン
ゼンテルリンfjJ Jを「p−メトキシベンゼンチル
リン酸無水物」に訂正する。2) Page 14, lines 2 to 3, "p-methoxyhensentellurin fjJ J" is corrected to "p-methoxybenzenethyl phosphoric anhydride."
以 上that's all
Claims (1)
メチルケトン類を製造するにあたり、下記一般式で表さ
れるアリールチルリン酸無水物の存在下でプロトンを供
給し得る化合物と該アセチレン化合物とを反応させるこ
とを特徴とするメチルケトン類の製造方法。 一般式:(式中、Ar−はアリール基 を表し、置換基を有しな いかまたは置換基を有す るものの中から選ばれる ものである。) 2)アリール基が、炭素数1〜8のアルキル基、アルコ
キシル基、置換または無置換アミノ基、置換または無置
換フェノキシ基、ベンジル基、ハロゲン原子からなる群
から選ばれた置換基1個または2個以上を有する置換体
である特許請求の範囲第1項記載の製造方法。[Scope of Claims] 1) A compound capable of supplying protons in the presence of an arylthylphosphoric anhydride represented by the following general formula when producing methyl ketones by adding water to a compound having a terminal acetylene bond. A method for producing methyl ketones, the method comprising reacting the acetylene compound with the acetylene compound. General formula: (In the formula, Ar- represents an aryl group, and is selected from those having no substituent or having a substituent.) 2) The aryl group is an alkyl group having 1 to 8 carbon atoms. , an alkoxyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted phenoxy group, a benzyl group, and a halogen atom. Manufacturing method described in section.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21805986A JPS6377834A (en) | 1986-09-18 | 1986-09-18 | Production of methyl ketones |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP21805986A JPS6377834A (en) | 1986-09-18 | 1986-09-18 | Production of methyl ketones |
Publications (1)
Publication Number | Publication Date |
---|---|
JPS6377834A true JPS6377834A (en) | 1988-04-08 |
Family
ID=16713999
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP21805986A Pending JPS6377834A (en) | 1986-09-18 | 1986-09-18 | Production of methyl ketones |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS6377834A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014168056A1 (en) * | 2013-04-11 | 2014-10-16 | セントラル硝子株式会社 | Method for producing 1,1,1,5,5,5-hexafluoroacetylacetone |
-
1986
- 1986-09-18 JP JP21805986A patent/JPS6377834A/en active Pending
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014168056A1 (en) * | 2013-04-11 | 2014-10-16 | セントラル硝子株式会社 | Method for producing 1,1,1,5,5,5-hexafluoroacetylacetone |
JP2014218495A (en) * | 2013-04-11 | 2014-11-20 | セントラル硝子株式会社 | Production method of 1,1,1,5,5,5-hexafluoroacetylacetone |
CN105102411A (en) * | 2013-04-11 | 2015-11-25 | 中央硝子株式会社 | Method for producing 1,1,1,5,5,5-hexafluoroacetylacetone |
US9409843B2 (en) | 2013-04-11 | 2016-08-09 | Central Glass Company, Limited | Method for producing 1,1,1,5,5,5-hexafluoroacetylacetone |
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