JP6751751B2 - ジイソブテンのＰｄ触媒によるヒドロキシカルボニル化工程（硫酸／配位子の比） - Google Patents
ジイソブテンのＰｄ触媒によるヒドロキシカルボニル化工程（硫酸／配位子の比） Download PDFInfo
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- FXNDIJDIPNCZQJ-UHFFFAOYSA-N 2,4,4-trimethylpent-1-ene Chemical compound CC(=C)CC(C)(C)C FXNDIJDIPNCZQJ-UHFFFAOYSA-N 0.000 title claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims description 14
- 239000003446 ligand Substances 0.000 title claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 7
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 4
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims description 4
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 101150003085 Pdcl gene Proteins 0.000 claims description 2
- RBYGDVHOECIAFC-UHFFFAOYSA-L acetonitrile;palladium(2+);dichloride Chemical compound [Cl-].[Cl-].[Pd+2].CC#N.CC#N RBYGDVHOECIAFC-UHFFFAOYSA-L 0.000 claims description 2
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 150000001735 carboxylic acids Chemical class 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000021523 carboxylation Effects 0.000 description 1
- 238000006473 carboxylation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000007248 oxidative elimination reaction Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 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
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/14—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on a carbon-to-carbon unsaturated bond in organic compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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Description
本発明は、ジイソブテンのＰｄ触媒によるヒドロキシカルボニル化工程（硫酸／配位子の比）に関する。
プロピオン酸、アジピン酸、脂肪酸を含むカルボン酸は、ポリマー、医薬品、溶媒、食品添加物の調製に用いられる。カルボン酸の入手手段としては、一般的に炭化水素、アルコール又はアルデヒドの酸化、オゾン分解によるオレフィンの酸化開裂、トリグリセリド、ニトリル、エステル又はアミドの加水分解、グリニャール試薬や有機リチウム試薬のカルボキシル化、ハロホルム反応におけるメチルケトンのハロゲン化とそれに次ぐ加水分解が挙げられる。
オレフィンのヒドロカルボキシル化は、カルボン酸を得るための方法として非常に有望且つ環境に優しい。ヨウ化物の存在下、メタノールをカルボニル化すると酢酸が生成される。コッホ反応では、水と一酸化炭素をアルケンに添加し、強塩基により触媒されて反応が進行する。この方法は、第二級又は第三級カルボカチオンを形成するアルケン、例えばイソブチレンからピバル酸を得る際に効果的である。ＣＯとＨ２Ｏをアルケン／アルキンに同時添加して生じるヒドロカルボキシル化は、直接的且つ簡便なカルボン酸の合成方法となる。
本発明の目的は、ジイソブテン（ＤＩＢＮ）のＰｄ触媒によるヒドロキシカルボニル化において、良好な転換率をもたらす工程を提供することとした。この反応は、単一のステップで行われるべきである。
請求項１に記載の工程により、この目的を達成する。
工程は、以下のステップを含む：
ジイソブテンを添加するステップａ）と、
錯体を形成できるＰｄを含む化合物を添加するステップｂ）と、
下記の配位子Ｌ１を添加するステップｃ）と、
酢酸を添加するステップｄ）と、
１モルの配位子Ｌ１当たり少なくとも３．５ｍｏｌの硫酸を添加するステップｅ）と、
ＣＯを供給するステップｆ）と、
反応混合物を加熱してジイソブテンを下記の化合物Ｐ１に転換させるステップｇ）。
ジイソブテンを添加するステップａ）と、
錯体を形成できるＰｄを含む化合物を添加するステップｂ）と、
下記の配位子Ｌ１を添加するステップｃ）と、
酢酸を添加するステップｄ）と、
１モルの配位子Ｌ１当たり少なくとも３．５ｍｏｌの硫酸を添加するステップｅ）と、
ＣＯを供給するステップｆ）と、
反応混合物を加熱してジイソブテンを下記の化合物Ｐ１に転換させるステップｇ）。
工程の一形態において、ステップｂ）の化合物は、ＰｄＣｌ２、ＰｄＢｒ２、Ｐｄ（ａｃａｃ）２、Ｐｄ（ｄｂａ）２（ｄｂａはジベンジリデンアセトン）、ＰｄＣｌ２（ＣＨ３ＣＮ）２から選択される。
工程の一形態において、ステップｂ）の化合物はＰｄ（ａｃａｃ）２である。
工程の一形態において、硫酸は、１モルの配位子Ｌ１当たり３．５ｍｏｌ〜５ｍｏｌの範囲の量で添加される。
工程の一形態において、硫酸は、１モルの配位子Ｌ１当たり３．５ｍｏｌ〜４．５ｍｏｌの範囲の量で添加される。
工程の一形態において、ステップｇ）では、反応混合物を８０℃〜１６０℃の温度、好ましくは１００℃〜１４０℃の温度に加熱する。
工程の一形態において、ステップｆ）では、反応が１０バール〜４０バール、好ましくは１０バール〜３０バールのＣＯ圧下で進むようにＣＯを供給する。
本発明を、以下の実施例によってより詳しく説明する。
４ｍｌのバイアルに、［Ｐｄ（ａｃａｃ）２］（１．７５ｍｇ、０．２５ｍｏｌ％）、Ｌ１（１１．８３ｍｇ、１．０ｍｏｌ％）、Ｈ２ＳＯ４（３．１ｍｇ、１．４ｍｏｌ％）、及びオーブンで乾燥済みの撹拌子を充填した。次いで、バイアルをセプタム（ＰＴＦＥ被覆スチレン−ブタジエンゴム）とフェノール樹脂キャップで密封した。その後、バイアルの排気とアルゴンの補充を３回繰り返した。さらに、Ｈ２Ｏ（０．２９ｍｌ）、酢酸（０．８５ｍｌ）、ジイソブテン（ＤＩＢＮ）（２．３ｍｍｏｌ）をシリンジによりバイアルに添加した。バイアルを合金板に載置し、アルゴン雰囲気下でＰａｒｒ Ｉｎｓｔｒｕｍｅｎｔ社の４５６０シリーズのオートクレーブ（３００ｍｌ）に移した。オートクレーブをＣＯにより３回フラッシュした後、ＣＯ圧を室温下１５バールまで上昇させ、続いてＮ２と共にＣＯ圧を２５バールまで上昇させた。反応は１２０℃で３時間続いた。反応の終了時に、オートクレーブを室温まで冷却し、注意深く減圧した。その後、イソオクタン（１００μｌ）を内部標準として添加した。ＧＣ分析により転換率を測定した。
Ｈ２ＳＯ４／Ｌ１の比を調整しながら前述の実験を繰り返した。それ以外のパラメータは全てそのまま維持した。
結果を次の表にまとめる。
以上の実験結果からも分かるように、本発明の工程によれば、前述の目的が達成される。
Claims (5)
- ジイソブテンを添加するステップａ）と、
錯体を形成できるＰｄを含む化合物を添加するステップｂ）と、
下記の配位子Ｌ１を添加するステップｃ）と、
１モルの配位子Ｌ１当たり少なくとも３．５ｍｏｌの硫酸を添加するステップｅ）と、
ＣＯを供給するステップｆ）と、
反応混合物を加熱して前記ジイソブテンを下記の化合物Ｐ１に転換させるステップｇ）と、
- ステップｂ）の前記化合物は、ＰｄＣｌ２、ＰｄＢｒ２、Ｐｄ（ａｃａｃ）２、Ｐｄ（ｄｂａ）２（ｄｂａはジベンジリデンアセトン）、ＰｄＣｌ２（ＣＨ３ＣＮ）２から選択される、請求項１に記載のジイソブテンのヒドロキシカルボニル化工程。
- 前記硫酸は、１モルの配位子Ｌ１当たり３．５ｍｏｌ〜５ｍｏｌの範囲の量で添加される、請求項１又は２に記載のジイソブテンのヒドロキシカルボニル化工程。
- 前記ステップｇ）において、前記反応混合物を８０℃〜１６０℃の温度に加熱する、請求項１〜３のいずれかに記載のジイソブテンのヒドロキシカルボニル化工程。
- 前記ステップｆ）において、前記反応が１０バール〜４０バールのＣＯ圧下で進むようにＣＯを供給する、請求項１〜４のいずれかに記載のジイソブテンのヒドロキシカルボニル化工程。
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