JPH0469351A - Production of 1,3-propanediol derivative - Google Patents
Production of 1,3-propanediol derivativeInfo
- Publication number
- JPH0469351A JPH0469351A JP2181890A JP18189090A JPH0469351A JP H0469351 A JPH0469351 A JP H0469351A JP 2181890 A JP2181890 A JP 2181890A JP 18189090 A JP18189090 A JP 18189090A JP H0469351 A JPH0469351 A JP H0469351A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- water
- formula
- compound
- washing
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical class C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 title claims description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 16
- 238000005882 aldol condensation reaction Methods 0.000 claims abstract description 10
- 150000007514 bases Chemical class 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 26
- 238000005406 washing Methods 0.000 abstract description 12
- 239000001257 hydrogen Substances 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 150000001299 aldehydes Chemical class 0.000 abstract description 8
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000004014 plasticizer Substances 0.000 abstract description 2
- 229920001225 polyester resin Polymers 0.000 abstract description 2
- 239000004645 polyester resin Substances 0.000 abstract description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 abstract 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 abstract 1
- 239000000920 calcium hydroxide Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- 239000000243 solution Substances 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 239000003921 oil Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 238000004817 gas chromatography Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- UNNGUFMVYQJGTD-UHFFFAOYSA-N 2-Ethylbutanal Chemical compound CCC(CC)C=O UNNGUFMVYQJGTD-UHFFFAOYSA-N 0.000 description 4
- LGYNIFWIKSEESD-UHFFFAOYSA-N 2-ethylhexanal Chemical compound CCCCC(CC)C=O LGYNIFWIKSEESD-UHFFFAOYSA-N 0.000 description 4
- -1 aldol compound Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- HSJKGGMUJITCBW-UHFFFAOYSA-N beta-hydroxybutyraldehyde Natural products CC(O)CC=O HSJKGGMUJITCBW-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- XRVCFZPJAHWYTB-UHFFFAOYSA-N prenderol Chemical compound CCC(CC)(CO)CO XRVCFZPJAHWYTB-UHFFFAOYSA-N 0.000 description 2
- OIQXFRANQVWXJF-LIQNAMIISA-N (1s,2z,4r)-2-benzylidene-4,7,7-trimethylbicyclo[2.2.1]heptan-3-one Chemical compound O=C([C@]1(C)CC[C@H]2C1(C)C)\C2=C/C1=CC=CC=C1 OIQXFRANQVWXJF-LIQNAMIISA-N 0.000 description 1
- BHVGMUDWABJNRC-UHFFFAOYSA-N (±)-2-methylhexanal Chemical compound CCCCC(C)C=O BHVGMUDWABJNRC-UHFFFAOYSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 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
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229950006800 prenderol Drugs 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyesters Or Polycarbonates (AREA)
- Phenolic Resins Or Amino Resins (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
Description
【発明の詳細な説明】
は前記と同義である）
プロパンジオール誘導体の製
本発明は、１．３−プロパンジオール誘導体の新規な製
造法に関する。DETAILED DESCRIPTION OF THE INVENTION has the same meaning as above) Production of propanediol derivatives The present invention relates to a novel method for producing 1,3-propanediol derivatives.
１３−プロパンジオール誘導体は、ポリエステル樹脂、
アルキッド樹脂、ポリウレタン樹脂、反応性モノマー、
可塑剤、合成、１１滑油、界面活性剤などの原料として
利用される。The 13-propanediol derivative is a polyester resin,
Alkyd resin, polyurethane resin, reactive monomer,
It is used as a raw material for plasticizers, synthetic oils, surfactants, etc.
従来の技術
１．３−プロパンジオールの製造１去として、相当する
アルデヒド′とホルムアルデヒドより塩基性あるいは酸
性の触媒の存在下にアルドール縮合反応させてアルドー
ル体を生成させ、次いで水素化する方法が知られてし）
る（例えば、特公昭６１−２６７６７号公報）。Prior art 1. Production of 3-propanediol As a first step, a method is known in which the corresponding aldehyde and formaldehyde are subjected to an aldol condensation reaction in the presence of a basic or acidic catalyst to produce an aldol compound, and then hydrogenated. )
(For example, Japanese Patent Publication No. 61-26767).
発明が解決しようとする課題
前記製造法におし）で、アルドール縮合反応液から水層
を分離後、あるいは有機溶媒を留去後に水層を分離する
だけで水素化工程に付すと、触媒活性を低下させ、水素
化反応の反応率および／または選択率が低く、工業的製
造法としては必ずしも有利な方法ではなく、さらにを利
な製法の開発が望まれている。Problems to be Solved by the Invention In the above-mentioned production method, if the aqueous layer is separated from the aldol condensation reaction solution or the aqueous layer is simply separated after distilling off the organic solvent and then subjected to the hydrogenation step, the catalytic activity is The reaction rate and/or selectivity of the hydrogenation reaction are low, and therefore it is not necessarily an advantageous method as an industrial production method, and there is a desire to develop a production method that is even more advantageous.
本発明は、アルドール縮合反応液を水素化工程に付す前
に水洗することにより、水素化反応の反応率および／ま
たは選択率が著しく向上するという知見にもとづくもの
である。The present invention is based on the finding that the reaction rate and/or selectivity of the hydrogenation reaction can be significantly improved by washing the aldol condensation reaction solution with water before subjecting it to the hydrogenation step.
課題を解決するための手段
本発明によれば１．３−プロパンジオール誘導体の良好
な収率で、工業的に実施可能な新規な製造法が提供され
る。Means for Solving the Problems According to the present invention, a novel industrially practicable manufacturing method is provided with a good yield of 1,3-propanediol derivatives.
即ち、本発明は式（１）
％式％（１）
（式中、Ｒ’ 、Ｒ２は同一または異−二って炭素数２
〜４のアルキル基を表わす〉で表わされるアルデヒドと
ホルムアルデヒドとを塩基性化合物の存在下にアルドー
ル縮合反応させ、該反応液を水洗した後に水素化反応に
付すことを特徴とする式（ＩＩ）
ＨＯＣＨ２ＣＣＨ２０Ｈ（ＩＩ）
（式中、Ｒ’ 、Ｒ２は前記と同義である）で表わされ
る１３−プロパンジオール誘導体の製造法に関する。That is, the present invention is based on the formula (1) % formula % (1) (wherein R' and R2 are the same or different, meaning carbon number 2
-4 representing an alkyl group> and formaldehyde are subjected to an aldol condensation reaction in the presence of a basic compound, and the reaction solution is washed with water and then subjected to a hydrogenation reaction.Formula (II) HOCH2CCH20H (II) A method for producing a 13-propanediol derivative represented by the formula (wherein R' and R2 have the same meanings as above).
ここで式日）、（ｎ）で表わされる化合物をそれぞれ化
合物（Ｉ）、（ＩＩ）という。他の式番号の化合物につ
いても同様である。Here, the compounds represented by (n) are referred to as compounds (I) and (II), respectively. The same applies to compounds having other formula numbers.
Ｒ’ 、Ｒ”の定義における炭素数２〜４のアルキル基
は、直鎮または分岐状のアルキル基、具体的には、エチ
ル、プロピル、イソプロピル、ブチル、イソブチル、ｔ
ｅｒｔ−ブチルなどがあげられる。The alkyl group having 2 to 4 carbon atoms in the definition of R' and R'' is a straight or branched alkyl group, specifically, ethyl, propyl, isopropyl, butyl, isobutyl, t
Examples include ert-butyl.
本発明による製造法は次の反応式で示される。The production method according to the present invention is shown by the following reaction formula.
Ｒ１塩基性化合物
ＣＨＣＨＯ↑ ＨＣＨ○
Ｒ’ ＲＨＯＣＨ２
ＣＣＨ○ □ＨＯＣＨ，ＣＣＨ，０）ｉＲ２Ｒ”
（Ｉ［Ｉ） （Ｉｔ）
（式中、Ｒ’ 、Ｒ２は前記と同義である）即ち、本反
応はアルデヒド（１）とホルムアルデヒドとを塩基性化
合物の存在下に交さアルドール縮合反応させてアルドー
ル（ＩＩＩ）を生成する工程、次いで化合物（Ｉ）を水
素化する工程の２工程により、１．３−プロパンジオー
ル（ＩＩ）を製造する方法である。R1 Basic compound CHCHO↑ HCH○ R' RHOCH2
CCH○ □HOCH,CCH,0)iR2R” (I[I) (It)
(In the formula, R' and R2 have the same meanings as above.) That is, this reaction is a step in which aldehyde (1) and formaldehyde are crossed in the presence of a basic compound and subjected to an aldol condensation reaction to produce aldol (III). This is a method for producing 1,3-propanediol (II) through two steps: , and then hydrogenating compound (I).
なお、本発明は化合物（ＩＩＩ）を生成させた後、水＆
操作を行うことにより、次の水素化工程を有利に行うこ
とができる。In addition, in the present invention, after producing compound (III), water &
By performing this operation, the next hydrogenation step can be carried out advantageously.
以下各々の工程および操作について詳細に説明する。Each step and operation will be explained in detail below.
ｌ）交さアルドール縮合反応工程
本発明に用いられる化合物（Ｉ）は、それ自体公知物質
で、比較的低廉に工業的規模での人手が可能である。l) Cross-aldol condensation reaction step Compound (I) used in the present invention is a known substance per se and can be produced manually on an industrial scale at relatively low cost.
ホルムアルデヒドの量は化合物（１）に対してモル比で
０．５〜３．０１好ましくは１．０〜２．０である。ホ
ルムアルデヒドは、３５〜３７重量％の濃度の通常市販
の水溶液がそのまま用いられる。The amount of formaldehyde is in a molar ratio of 0.5 to 3.01, preferably 1.0 to 2.0, relative to compound (1). For formaldehyde, a commercially available aqueous solution having a concentration of 35 to 37% by weight is used as it is.
使用される塩基性化合物としては、水酸化ナトリウム、
水酸化カリウムなどのアルカリ金属水酸化物、水酸化力
ルンウム、水酸化マグネシウムなどのアルカリ土類金属
水酸化物、トリエチルアミン、トリブチルアミンなどの
三級アミンおよび強塩基性イオン交換樹脂などがあげら
れる。塩基性化合物の量は、化合物（１）に対してモル
比で００１〜０．３、好ましくは０．０３〜０．２であ
る。Basic compounds used include sodium hydroxide,
Examples include alkali metal hydroxides such as potassium hydroxide, alkaline earth metal hydroxides such as magnesium hydroxide, tertiary amines such as triethylamine and tributylamine, and strongly basic ion exchange resins. The amount of the basic compound is in a molar ratio of 0.001 to 0.3, preferably 0.03 to 0.2, relative to compound (1).
強塩基性陰イオン交換樹脂は反応混合液の全量に対して
５〜５０重量％、好ましくは１０〜４０重量％が用いら
れ、回分方式および連続方式のいずれでても行い得る。The amount of the strongly basic anion exchange resin used is 5 to 50% by weight, preferably 10 to 40% by weight, based on the total amount of the reaction mixture, and the reaction can be carried out either batchwise or continuously.
原料として用５する化合物（Ｉ）および生成化合物（Ｉ
ＩＩ）はいずれも実質的に水に不溶であるので前記のモ
ル比範囲内で反応液は不均一である。反応は不均一でも
進行するが、水溶性の有機溶媒を加えることにより促進
される。水溶性の有機溶媒としては、例えばメタノーノ
ペエタノール、プロパツールなどのアルコール類、ジメ
トキンエタン、ジオキサンなどのエーテル類が好適に用
いられる。Compound (I) used as a raw material and product compound (I
Since all of II) are substantially insoluble in water, the reaction solution is non-uniform within the above molar ratio range. Although the reaction proceeds even if it is heterogeneous, it is accelerated by adding a water-soluble organic solvent. As the water-soluble organic solvent, for example, alcohols such as methanol, propatool, etc., and ethers, such as dimethyneethane and dioxane, are preferably used.
有機溶媒の添加量は特に制限されないが、化合物（１）
とホルムアルデヒドとの仕込み合計に対して８０重量％
以下で十分である。反応は、塩基性化合物の種類によっ
て異なるが、一般に１５〜１２０℃の温度範囲で行われ
、塩基性化合物の種類、量、反応温度によって異なるが
、通常１−１０時間で完了する。Although the amount of organic solvent added is not particularly limited, compound (1)
80% by weight based on the total amount of formaldehyde and
The following is sufficient. The reaction is generally carried out in a temperature range of 15 to 120°C, although it varies depending on the type of basic compound, and is usually completed in 1 to 10 hours, although it varies depending on the type and amount of the basic compound and the reaction temperature.
２）水洗操作
次いで、交さアルドール縮合反応液から水層を分離後、
あるいは有機溶媒を留去後に水層を分離後、さらに油層
を水洗することにより、未反応のホルムアルデヒドや副
生ずる不純物が除去され、触媒活性の低下が防止できる
。2) Water washing operation Then, after separating the aqueous layer from the crossed aldol condensation reaction solution,
Alternatively, by distilling off the organic solvent, separating the aqueous layer, and then washing the oil layer with water, unreacted formaldehyde and by-product impurities are removed, and a decrease in catalyst activity can be prevented.
水洗に使用される水の量、水洗の回数は特に制限されな
いが、油層の量に対して０．３〜１．５倍の量で１〜５
回で十分である。The amount of water used for water washing and the number of times of water washing are not particularly limited, but the amount is 0.3 to 1.5 times the amount of the oil layer.
times is sufficient.
水洗するときの温度は、通常１０〜９０℃、好ましくは
２０〜７０℃の範囲である。水洗の時間は、−回当たり
５〜６０分、好ましくは１０〜３０分である。The temperature when washing with water is usually in the range of 10 to 90°C, preferably 20 to 70°C. The time for washing with water is 5 to 60 minutes, preferably 10 to 30 minutes.
３）水素化工程
水素化反応は、それ自体公知の方法で行われ、水素共存
下において適当な溶媒に溶解した化合物（ＩＩＩ）の溶
液中に水素化触媒を分散または懸濁させるか、あるいは
該触媒を充填したカラムに化合物（［１）の溶液を供給
する方法により行われる。3) Hydrogenation step The hydrogenation reaction is carried out by a method known per se, by dispersing or suspending a hydrogenation catalyst in a solution of compound (III) dissolved in an appropriate solvent in the presence of hydrogen, or This is carried out by supplying a solution of compound ([1) to a column filled with a catalyst.
適当な溶媒としては、水素化反応に不活性であり厚化合
物（ＩＩ［）を溶解するものであれば特に制限されない
が、メタノール、エタノール、プロパツールなどのアル
コール類が特に好ましい。Suitable solvents are not particularly limited as long as they are inert to the hydrogenation reaction and dissolve the thick compound (II[), but alcohols such as methanol, ethanol, and propatool are particularly preferred.
使用し得る好適な水素化触媒としては、ニッケル、ルテ
ニウム、白金、銅、ロジウムなどの金属の１種または２
種以上を触媒活性成分として含有するものがあげられる
。また、これらの金属にクロム、亜鉛、バリウム、アル
ミニウム、マグネシウム、タングステンなどの金属を更
なる成分として含有するものも好適な触媒としてあげら
れる。Suitable hydrogenation catalysts that can be used include one or two metals such as nickel, ruthenium, platinum, copper, and rhodium.
Examples include those containing at least one species as a catalytically active component. Suitable catalysts include those containing metals such as chromium, zinc, barium, aluminum, magnesium, and tungsten as additional components in addition to these metals.
般に、水素化反応は５０〜２００℃、好ましくは８０〜
１５０℃の温度範囲で、１〜１５０ｋｇ／ｃａｔ。Generally, the hydrogenation reaction temperature is 50-200°C, preferably 80-200°C.
1 to 150 kg/cat in a temperature range of 150°C.
好ましくは５〜８０ｋｇ／ｃｕｔの水素圧で行われる。Preferably, the hydrogen pressure is 5 to 80 kg/cut.
水素化反応は、例えば攪拌オートクレーブまたは反応管
中において連続式または回分式のいずれの方法によって
も行し）得る。The hydrogenation reaction can be carried out either continuously or batchwise, for example in a stirred autoclave or reaction tube.
反応終了後、反応液から通常の方法により目的とする化
合物（ＩＩ）を単離精製することができる。After the reaction is completed, the target compound (II) can be isolated and purified from the reaction solution by a conventional method.
例えば、目的化合物が液体の場合、触媒から分離された
反応液中の低沸点化合物を常圧または減圧下に留去し、
続いて目的の化合物（ＩＩ）を含有する残渣を減圧蒸留
することにより目的化合物（Ｉｔ）が分離される。ある
いは、目的化合物が固体の場合、低沸点化合物を減圧下
に留去後、トルエンやヘキサンなどの適当な溶媒から結
晶化させて化合物（ＩＩ）を分離することもできる。For example, when the target compound is a liquid, low-boiling compounds in the reaction solution separated from the catalyst are distilled off under normal pressure or reduced pressure,
Subsequently, the residue containing the target compound (II) is distilled under reduced pressure to separate the target compound (It). Alternatively, when the target compound is a solid, compound (II) can be separated by distilling off the low-boiling point compound under reduced pressure and then crystallizing it from a suitable solvent such as toluene or hexane.
以下の実施例および比較例により本発明の詳細な説明す
る。The present invention will be explained in detail by the following examples and comparative examples.
実施例１
２−エチルブチルアルデヒド６０．２ｇ＜０．６モル）
、３７％ホルマリン水溶液３２．４ｇ（０，４モル）、
メタノール４５ｍ１および２５％水酸化ナトリウム水溶
液５．７６ ｇ （０，０３６モル）の混合液を５０℃
で２時間加熱攪拌した。反応後、メタノールを減圧下留
去し、水層を除去し、油層をヘキサン４０ｍ１で希釈し
た後、水６０ｍ１２で２回洗浄した。油層からヘキサン
および過剰の２−エチルブチルアルデヒドを減圧留去し
、残渣４７．２ ｇを得た。得られた残渣をメタノール
６０＋ｎ＆に溶解し、う不一ニッケル２３ｇと共に２０
０−のオートクレーブに仕込み、水素圧を６０ｋｇ／Ｃ
ｒｌに保ちながら１００℃で７時間加熱撹拌した。反応
終了後、反応液をガスクロマトグラフィーにより分析し
たところ、２．２−ジエチル−１，３−プロパンジオー
ル４２．３ｇ（収率８０％）であった。Example 1 2-ethylbutyraldehyde 60.2g<0.6mol)
, 32.4 g (0.4 mol) of 37% formalin aqueous solution,
A mixture of 45 ml of methanol and 5.76 g (0,036 mol) of 25% aqueous sodium hydroxide solution was heated at 50°C.
The mixture was heated and stirred for 2 hours. After the reaction, methanol was distilled off under reduced pressure, the aqueous layer was removed, the oil layer was diluted with 40 ml of hexane, and then washed twice with 60 ml of water. Hexane and excess 2-ethylbutyraldehyde were distilled off under reduced pressure from the oil layer to obtain 47.2 g of a residue. The obtained residue was dissolved in methanol 60 + n&, and 20
0- in an autoclave and set the hydrogen pressure to 60kg/C.
The mixture was heated and stirred at 100° C. for 7 hours while maintaining the temperature at rl. After the reaction was completed, the reaction solution was analyzed by gas chromatography and found to be 42.3 g (yield: 80%) of 2,2-diethyl-1,3-propanediol.
ガスクロマトグラフィーσ液層：ユニソール３０７２％
、ユニポートＨＰ （６０／８０）、３．２ｍｍφ×５
ｍカラム温度；５０〜２２０℃（１０℃／ｍ１ｎ）；注
入温度２３０℃、内部標準、ジエチレングリコールジメ
チルエーテル〕
以下の実施例および比較例に示すガスクロマトグラフィ
ーの条件は実施例１のときと同様である。Gas chromatography σ liquid layer: Unisol 3072%
, Uniport HP (60/80), 3.2mmφ×5
m column temperature; 50 to 220°C (10°C/m1n); injection temperature 230°C, internal standard, diethylene glycol dimethyl ether] The gas chromatography conditions shown in the following examples and comparative examples are the same as in Example 1. .
比較例１
２−エチルブチルアルデヒド６０．２ｇ（０，６モル）
、３７％ホルマリン水溶液３２．４ｇ（０，４モル）、
メタノール４５−および２５％水酸化ナトリウム水溶液
５．７６ ｇ （０，０３６モル）の混合液を５０℃で
２時間加熱攪拌した。反応後、メタノールおよび過剰の
２−エチルブチルアルデヒドを減圧留去し、得られた残
渣５３．８ ｇを再度メタノール６０ｍに溶解させた。Comparative example 1 2-ethylbutyraldehyde 60.2g (0.6 mol)
, 32.4 g (0.4 mol) of 37% formalin aqueous solution,
A mixed solution of 45% methanol and 5.76 g (0,036 mol) of 25% aqueous sodium hydroxide solution was heated and stirred at 50° C. for 2 hours. After the reaction, methanol and excess 2-ethylbutyraldehyde were distilled off under reduced pressure, and 53.8 g of the resulting residue was dissolved again in 60 ml of methanol.
この溶液をラネーニッケル２．３ｇと共に２００ｍ１の
オートクレーブに仕込み、水素圧を６０ｋｇ／ｃｕｔに
保ちながら１００℃で７時間加熱攪拌した。反応液をガ
スクロマトグラフィーにより分析したところ、２．２−
ジエチル１．３−プロパンジオール７．９ｇ（収率１５
％）であった。This solution was charged into a 200 ml autoclave together with 2.3 g of Raney nickel, and heated and stirred at 100° C. for 7 hours while maintaining the hydrogen pressure at 60 kg/cut. When the reaction solution was analyzed by gas chromatography, 2.2-
7.9 g of diethyl 1,3-propanediol (yield: 15
%)Met.
実施例２
２−エチルヘキシルアルデヒド７６．９ｇ（０，６モル
）、３７％ホルマリン水溶液３２．４ｇ（０，４モル）
およびメタノール８０ゴの混合液を７０℃に保ちながら
２５％水酸化ナトリウム水溶液６．４ｇ（０，０４モル
）を１５分で滴下し、続いて７０℃で３時間加熱攪拌し
た。反応後、メタノールを減圧留去し、水層を除去し、
油層を水４５ｄで２回洗浄した後、油層を減圧ａｔｉＬ
残渣７１．０ ｇを得た。得られた残渣の内１０． Ｏ
ｇをメタノール１０ｍ１に溶解させ、ニッケル触媒Ｎ−
１０３０（日揮化学社製）２．０ｇと共に１００ｍ１の
オートクレーブに仕込み、水素圧を２０ｋｇ／ｃｕｔに
保ちながら１２０℃で２時間加熱攪拌した。Example 2 76.9 g (0.6 mol) of 2-ethylhexylaldehyde, 32.4 g (0.4 mol) of 37% formalin aqueous solution
6.4 g (0.04 mol) of a 25% aqueous sodium hydroxide solution was added dropwise to the mixture of 80 g of methanol and 70° C. over 15 minutes, followed by heating and stirring at 70° C. for 3 hours. After the reaction, methanol was distilled off under reduced pressure and the aqueous layer was removed.
After washing the oil layer twice with 45 d of water, the oil layer was reduced to atiL.
71.0 g of residue was obtained. Of the obtained residue, 10. O
Dissolve g in methanol 10ml, add nickel catalyst N-
1030 (manufactured by JGC Chemical Co., Ltd.) in a 100 ml autoclave, and heated and stirred at 120° C. for 2 hours while maintaining the hydrogen pressure at 20 kg/cut.
反応液をガスクロマトグラフィーにより分析したところ
、２−ブチル−２−エチル−１，３−プロパンジオール
７．４ｇ（収率８２％）であった。When the reaction solution was analyzed by gas chromatography, it was found to be 7.4 g (yield: 82%) of 2-butyl-2-ethyl-1,3-propanediol.
比較例２
２−エチルヘキシルアルデヒド７６．９ｇ（０，６モル
）、３７％ホルマリン水溶液３２．４ｇ（０，４モル）
およびメタノール８０−の混合液を７０℃に保ちながら
２５％水酸化ナトリウム水溶液６．４ｇ（０，０４モル
）を１５分で滴下し、続いて７０℃で３時間加熱攪拌し
た。反応後、反応液１８０ｇの内２０ｇを、ニッケル触
媒Ｎ−１０３■２．Ｏｇと共に１００ｍｆ！のオートク
レーブに仕込み、水素圧を２０ｋｇ／ｃｕｔに保ちなが
ら１２０℃で２時間加熱攪拌した。反応液をガスクロマ
トグラフィーにより分析した出ころ、２−ブチル−２−
エチル１．３−プロパンジオール０．７ｇ（収率ｌＯ％
）であった。Comparative Example 2 76.9 g (0.6 mol) of 2-ethylhexylaldehyde, 32.4 g (0.4 mol) of 37% formalin aqueous solution
6.4 g (0.04 mol) of a 25% aqueous sodium hydroxide solution was added dropwise to the mixture of 80° C. and methanol over 15 minutes while maintaining the temperature at 70° C., followed by heating and stirring at 70° C. for 3 hours. After the reaction, 20g of the 180g of the reaction solution was added to the nickel catalyst N-1032. 100mf with Og! The mixture was charged into an autoclave, and heated and stirred at 120° C. for 2 hours while maintaining the hydrogen pressure at 20 kg/cut. The reaction solution was analyzed by gas chromatography, and the result was 2-butyl-2-
Ethyl 1.3-propanediol 0.7 g (yield lO%
)Met.
比較例３
２−エチルヘキシルアルデヒド７６．９ｇ（０，６モル
）、３７％ホルマリン水溶液３２．４ｇ（０，４モル）
およびメタノール８０−の混合液を７０℃に保ちながら
２５％水酸化ナトリウム水溶液６．４ｇ（０，０４モル
）を１５分で滴下し、続いて７０℃で３時間加熱攪拌し
た。反応後、反応液１８０ｇの内１００ｇからメタノー
ルを減圧留去し、水層を除去した。油層５５．３ ｇを
メタノール７０ｍ１に溶解させ、ニッケル触媒Ｎ−１０
３０５，５ｇと共に３００ｍ１のオートクレーブに仕込
み、水素圧を２０ｋｇ／ｃ＋＋ｆに保ちながら１２０℃
で２時間加熱攪拌した。Comparative Example 3 76.9 g (0.6 mol) of 2-ethylhexylaldehyde, 32.4 g (0.4 mol) of 37% formalin aqueous solution
6.4 g (0.04 mol) of a 25% aqueous sodium hydroxide solution was added dropwise to the mixture of 80° C. and methanol over 15 minutes while maintaining the temperature at 70° C., followed by heating and stirring at 70° C. for 3 hours. After the reaction, methanol was distilled off under reduced pressure from 100 g of the 180 g of the reaction solution, and the aqueous layer was removed. Dissolve 55.3 g of the oil layer in 70 ml of methanol and add nickel catalyst N-10.
Charge 305.5g into a 300ml autoclave and heat at 120°C while maintaining hydrogen pressure at 20kg/c++f.
The mixture was heated and stirred for 2 hours.
反応液をガスクロマトグラフィーにより分析したところ
、２−ブチル−２−エチル−１，３−プロパンジオール
６．４ｇ（収率１８％）であった。When the reaction solution was analyzed by gas chromatography, it was found to be 6.4 g (yield: 18%) of 2-butyl-2-ethyl-1,3-propanediol.
実施例３
窒素置換した２００βの反応器に２−エチルヘキシルア
ルデヒド５７．７ｋｇ（４５０モル）、３７％ホルマリ
ン水溶液２４．３ｋｇ（３００モル）およびメタノール
６５ｆを仕込み、この混合液中に７０℃に保ちｍ＝から
２５％水酸化ナトリウム水溶液４．８ｋｇ（３０モル）
を５５分で滴下し、続いて７０℃でＪ時間加執攪拌した
。反応後、メタノールを減圧留去し、残渣に水３６．１
ｋｇを加えて水洗を行った。水層を除去した後、油層
に水３６．１ ｋｇを加えて再度水洗を行った。油１を
減圧濃縮することにより残渣５５．４ ｋｇを得た。二
の残渣をメタノール５０ｋｇに溶解させ、ガスクロマト
グラフィーにより分析したよころ、２−エチル−２−ヒ
ドロキンメチルヘキサナール３５．６ ｋｇであった。Example 3 57.7 kg (450 mol) of 2-ethylhexylaldehyde, 24.3 kg (300 mol) of a 37% formalin aqueous solution, and 65 f of methanol were charged into a 200 β reactor purged with nitrogen, and the mixture was kept at 70°C. = 25% aqueous sodium hydroxide solution 4.8 kg (30 mol)
was added dropwise over 55 minutes, followed by stirring at 70° C. for J hours. After the reaction, methanol was distilled off under reduced pressure, and 36.1% of water was added to the residue.
kg was added and washed with water. After removing the aqueous layer, 36.1 kg of water was added to the oil layer to perform water washing again. Oil 1 was concentrated under reduced pressure to obtain 55.4 kg of residue. The residue from step 2 was dissolved in 50 kg of methanol and analyzed by gas chromatography, which revealed that it was 35.6 kg of 2-ethyl-2-hydroquine methylhexanal.
この溶液を、固定床用う不一ニッケルＲ−２００Ｌ■（
日興リカ社製）７０−が充填された内径２１即、塔長４
００Ｍの反応管に水素圧が５０ｋｇ／ｃａｔになるよう
に制御しながら水素を供給させると同時に、液空間速度
（ＬＳＶ）０．４５Ｈｒ−’の流量で連続的に供給させ
た。この間、反応管の中段の温度をほぼ１２０℃に保っ
た。Add this solution to Ufuichi Nickel R-200L for fixed bed (
(manufactured by Nikko Rica) filled with 70- inner diameter 21, tower length 4
Hydrogen was supplied to the 00M reaction tube while controlling the hydrogen pressure to be 50 kg/cat, and simultaneously supplied continuously at a flow rate of liquid hourly space velocity (LSV) of 0.45 Hr-'. During this time, the temperature at the middle stage of the reaction tube was maintained at approximately 120°C.
上記の操作による２−エチル−２−ヒドロキンメチルヘ
キサナールの反応率ヨ、２−ブチル−２エチル−１３−
プロパンジオールへの選択率を第１表に示す。Reaction rate of 2-ethyl-2-hydroquinemethylhexanal by the above procedure, 2-butyl-2ethyl-13-
The selectivity to propanediol is shown in Table 1.
第 １ 表
発明の効果
本発明により、安価な原料から収率良＜１．３プロパン
ジオ一ル誘導体を製造することができる。Table 1 Effects of the Invention According to the present invention, a propanediol derivative of <1.3 can be produced in good yield from inexpensive raw materials.
＼、−２／
なお、反応率と選択率は、流通系の反応を定常状態であ
るとみなし、人出口での単位時間当りの重量変化が無い
と仮定して、次の計算式により算出した。\, -2/ The reaction rate and selectivity were calculated using the following formula, assuming that the reaction in the distribution system is in a steady state and that there is no change in weight per unit time at the exit. .
手続 補 正 １！ｌ（自発：ｌ
平成２年／７月８日
１事件の表示
平成２ 年特”ｆｕ第１８１８９０ 号２発明の名称
１．３−プロパンジオール誘導体の製造法３補正をする
者
事件との関係 特許出願人
（Ｉ）の量はホルムアルデヒドに対して二に訂正する。Procedure amendment 1! l (Spontaneous: l July 8, 1990 1 Indication of case 1990 special "fu No. 181890 2 Name of invention 1. Process for producing 3-propanediol derivatives 3 Person making amendments Relationship with case Patent Applicant (I)'s amounts are corrected by two for formaldehyde.
′２）同書第９頁４行目の「目的化合物が液体の場合、
」を削除する。'2) On page 9, line 4 of the same book, ``If the target compound is a liquid,
” to be deleted.
名称 協和油化株式会社Name: Kyowa Yuka Co., Ltd.
Claims (1)
〜４のアルキル基を表わす）で表わされるアルデヒドと
ホルムアルデヒドとを塩基性化合物の存在下にアルドー
ル縮合反応させ、該反応液を水洗した後に水素化反応に
付すことを特徴とする式（II） ▲数式、化学式、表等があります▼（II） （式中、Ｒ＾１、Ｒ＾２は前記と同義である）で表わさ
れる１，３−プロパンジオール誘導体の製造法。[Claims] Formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R^1 and R^2 are the same or different and have 2 carbon atoms.
-4 representing an alkyl group) and formaldehyde are subjected to an aldol condensation reaction in the presence of a basic compound, and the reaction solution is washed with water and then subjected to a hydrogenation reaction.Formula (II) ▲ There are mathematical formulas, chemical formulas, tables, etc.▼(II) A method for producing a 1,3-propanediol derivative represented by (in the formula, R^1 and R^2 have the same meanings as above).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2181890A JPH0469351A (en) | 1990-07-10 | 1990-07-10 | Production of 1,3-propanediol derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2181890A JPH0469351A (en) | 1990-07-10 | 1990-07-10 | Production of 1,3-propanediol derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0469351A true JPH0469351A (en) | 1992-03-04 |
Family
ID=16108674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2181890A Pending JPH0469351A (en) | 1990-07-10 | 1990-07-10 | Production of 1,3-propanediol derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0469351A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391075A (en) * | 2011-08-08 | 2012-03-28 | 河北科技大学 | Preparation method of 1-aryl-2,2-dimethyl-1,3-propylene glycol |
-
1990
- 1990-07-10 JP JP2181890A patent/JPH0469351A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102391075A (en) * | 2011-08-08 | 2012-03-28 | 河北科技大学 | Preparation method of 1-aryl-2,2-dimethyl-1,3-propylene glycol |
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