CN101186604B - One-step method for synthesizing lactone type crown ether by lactone ring expansion - Google Patents
One-step method for synthesizing lactone type crown ether by lactone ring expansion Download PDFInfo
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- CN101186604B CN101186604B CN2007101905400A CN200710190540A CN101186604B CN 101186604 B CN101186604 B CN 101186604B CN 2007101905400 A CN2007101905400 A CN 2007101905400A CN 200710190540 A CN200710190540 A CN 200710190540A CN 101186604 B CN101186604 B CN 101186604B
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- lactone
- crown ether
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- epoxy alkane
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Abstract
The invention relates to a method for synthesizing lactone crown ether from lactone via ring enlargement one-step method, belonging to organic synthesis technical field. The invention uses lactone starting agent, at 100-200DEG C and 0.3-3.0MPa, to catalyze alkylene oxide via Al-Mg based compound catalyst to enlarge the ring of lactone, to synthesize lactone crown ether via one-step. The invention has simple and quick process, high conversion rate, eliminated diluent, non waste discharge and environment friend, which can significantly reduce the synthesis time, as one safe, effective and energy-saving technique.
Description
Technical field
A kind of lactone belongs to technical field of organic synthesis through the method for the synthetic lactone type crown ether of ring expansion single stage method.Specifically be initiator, under 100～200 ℃ and 0.3～3.0MPa condition, make the lactone ring expansion, the method for the synthetic lactone type crown ether of single stage method with Al-Mg based compound catalyst catalysis epoxy alkane with the lactone.
Background technology
The lactone type crown ether mainly adopts the cyclization of acyclic initiator, generally realizes by the acidylate annulation of binary carboxylic acid halides and multiethylene-glycol or dicarboxylate and dihalo multiethylene-glycol.But the reaction of this class often need carried out the intermolecular linear polymerization of ability inhibition in a large amount of solvents, and synthetic agent costliness, process loaded down with trivial details consuming time, environment friendly is poor.Huang Zaifu (Huang Zaifu. the quick novel method of the synthetic crown ether of the synthetic II. tube method of crown compound. chemical journal, 1981,39 (6): 579-580) wait the synthetic lactone type crown ether of employing tube method, though the reaction times is shortened, but still need make thinner with a large amount of benzene.Yet there are no the report of solvent-free synthetic lactone type crown ether.
We embed reaction (the Xia Y M of chain carboxylicesterss such as ethyl acetate with Al-Mg based composite catalyst catalysis epoxy alkane in previous work, Shen Y A, Fang Y, et al.One-step Production ofAlkoxylated Ethyl Acetate with Narrow Adduct Distribution.J of Chem Technologyand Biotechnology, 2006,82 (1): 47-50), but yet there are no the report that epoxy alkane embeds cyclic carboxylic esters.
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing the synthetic lactone type crown ether of ring expansion single stage method of lactone, be to overcome and have into the deficiency that cyclization becomes technology now, provide a kind of operational path weak point, environmental friendliness, need not thinner, the method that can synthesize the lactone type crown ether fast.
Technical scheme of the present invention: a kind of lactone is through the method for the synthetic lactone type crown ether of ring expansion single stage method, with the lactone is initiator, under 100～200 ℃ and 0.3～3.0MPa condition, make the lactone ring expansion with Al-Mg based compound catalyst catalysis epoxy alkane, single stage method is synthesized the lactone type crown ether;
Lactone and Al-Mg based composite catalyst are added in the potheater, and the add-on of catalyzer is 0.5%～5.0% of lactone and an epoxy alkane reactant total mass, uses N behind the airtight kettle cover
2Displacement gas reactor 3 times, behind reacting by heating thing to 100～200 ℃, drip the epoxy alkane of required adduct number molar weight while stirring, keep pressure at 0.3～3.0MPa, finish reaction after keeping reaction 30～60min after epoxy alkane dropwises again, filtered while hot is removed catalyzer and is made lactone type crown ether product.
The raw material lactone (1) that is adopted, epoxy alkane (2) and institute's synthetic product lactone type crown ether (3) have following structure:
N=1 in the formula～30, R
1=H, CH
3, CH
2CH
3, m=1,2,3, when m=1, R=H or carbonatoms are 1～8 straight chained alkyl; When m=2 or 3, R=H.
Beneficial effect of the present invention:
(1) the present invention directly synthesizes the lactone type crown ether through the ring expansion single stage method by the annular lactone raw material, and the reaction conditions gentleness is simple and efficient, the transformation efficiency height.Can shorten the reaction times greatly, cut down the consumption of energy.
(2) method provided by the invention need not add thinner, and no discharge helps environmental friendliness.
(3) with the ring expansion of Al-Mg based composite catalyst catalysis epoxy alkane to lactone, single stage method is synthesized the lactone type crown ether, and this will provide a kind of novel method for lactone type crown ether synthetic.
Specific implementation method
Below the present invention is carried out the description of embodiment, specific embodiment is as follows:
The preparation of Al-Mg based composite catalyst: with reference to the disclosed content of Chinese patent CN200510038866.2 that proposes by the applicant.
Embodiment 1:17-octyl group-1,4,7,10,13-five oxygen ring heptadecane-14-ketone synthetic
1mol γ-dodecalactone and Al-Mg based composite catalyst are added in the potheater, and the add-on of catalyzer is 1% of a reactant total mass.Use N behind the airtight kettle cover
2Displacement gas reactor 3 times.Behind reacting by heating thing to 100～105 ℃, drip 4mol oxyethane under 0.5～0.6MPa while stirring.Oxyethane finishes reaction after dropwising and keeping reaction 30min again, and filtered while hot is removed catalyzer.The transformation efficiency of γ-dodecalactone reaches 80.4%.
Embodiment 2:3,6-dimethyl-1,4,7-three oxygen ring undecane-8-ketone synthetic
1mol gamma-butyrolactone and Al-Mg based composite catalyst are added in the potheater, and the add-on of catalyzer is 0.5% of a reactant total mass.Use N behind the airtight kettle cover
2Displacement gas reactor 3 times.Behind reacting by heating thing to 140～145 ℃, drip the 2mol propylene oxide under 0.3～0.4MPa while stirring.Propylene oxide finishes reaction after dropwising and keeping reaction 30min again, and filtered while hot is removed catalyzer.The transformation efficiency of gamma-butyrolactone reaches 85.4%.
Embodiment 3:3,6,9,12-tetraethyl--1,4,7,10,13-five oxygen ring heptadecane-14-ketone synthetic
1mol 6-caprolactone and Al-Mg based composite catalyst are added in the potheater, and the add-on of catalyzer is 3% of a reactant total mass.Use N behind the airtight kettle cover
2Displacement gas reactor 3 times.Behind reacting by heating thing to 195～200 ℃, drip the 4mol butylene oxide ring under 2.9～3.0MPa while stirring.Butylene oxide ring finishes reaction after dropwising and keeping reaction 60min again, and filtered while hot is removed catalyzer.The transformation efficiency of 6-caprolactone reaches 68.4%.
Embodiment 4:1,4,7,10,13,16,19,22,25,28,31-11 oxygen ring pentatriacontane-32-ketone synthetic
1mol gamma-butyrolactone and Al-Mg based composite catalyst are added in the potheater, and the add-on of catalyzer is 5% of a reactant total mass.Use N behind the airtight kettle cover
2Displacement gas reactor 3 times.Behind reacting by heating thing to 165～170 ℃, drip 10mol oxyethane under 1.0～1.1MPa while stirring.Oxyethane finishes reaction after dropwising and keeping reaction 60min again, and filtered while hot is removed catalyzer.The transformation efficiency of gamma-butyrolactone reaches 88.1%.
Embodiment 5:1,4,7,10,13,16,19,22,25,28,31,34,37,40,43,46,49,52,55,58,61,64,67,70,73,76,79,82,85,88,91-hentriaconta-oxygen ring nine pentadecanes-92-ketone synthetic
1mol gamma-butyrolactone and Al-Mg based composite catalyst are added in the potheater, and the add-on of catalyzer is 5% of a reactant total mass.Use N behind the airtight kettle cover
2Displacement gas reactor 3 times.Behind reacting by heating thing to 165～170 ℃, drip 30mol oxyethane under 2.9～3.0MPa while stirring.Oxyethane finishes reaction after dropwising and keeping reaction 60min again, and filtered while hot is removed catalyzer.The transformation efficiency of gamma-butyrolactone reaches 78.7%.
Embodiment 6:50-methyl isophthalic acid, 4,7,10,13,16,19,22,25,28,31,34,37,40,43,46-16 oxygen ring pentacontane-47-ketone synthetic
1mol γ-Wu Neizhi and Al-Mg based composite catalyst are added in the potheater, and the add-on of catalyzer is 5% of a reactant total mass.Use N behind the airtight kettle cover
2Displacement gas reactor 3 times.Behind reacting by heating thing to 195～200 ℃, drip 15mol oxyethane under 2.9～3.0MPa while stirring.Oxyethane finishes reaction after dropwising and keeping reaction 60min again, and filtered while hot is removed catalyzer.The transformation efficiency of γ-Wu Neizhi reaches 86.3%.
Claims (1)
1. a lactone is through the method for the synthetic lactone type crown ether of ring expansion single stage method, it is characterized in that with the lactone being initiator, under 100～200 ℃ and 0.3～3.0MPa condition, make the lactone ring expansion with Al-Mg based compound catalyst catalysis epoxy alkane, single stage method is synthesized the lactone type crown ether;
Lactone and Al-Mg based composite catalyst are added in the potheater, and the add-on of catalyzer is 0.5%～5.0% of lactone and an epoxy alkane reactant total mass, uses N behind the airtight kettle cover
2Displacement gas reactor 3 times, behind reacting by heating thing to 100～200 ℃, drip the epoxy alkane of required adduct number molar weight while stirring, keep pressure at 0.3～3.0MPa, finish reaction after keeping reaction 30～60min after epoxy alkane dropwises again, filtered while hot is removed catalyzer and is made lactone type crown ether product;
Above-mentioned raw materials lactone (1), epoxy alkane (2) and institute's synthetic product lactone type crown ether (3) have following structure:
N=1 in the formula～30, R
1=H, CH
3, CH
2CH
3, m=1,2,3; When m=1, R=H or carbonatoms are 1～8 straight chained alkyl; When m=2 or 3, R=H.
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| CN2007101905400A CN101186604B (en) | 2007-11-30 | 2007-11-30 | One-step method for synthesizing lactone type crown ether by lactone ring expansion |
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| CN2007101905400A CN101186604B (en) | 2007-11-30 | 2007-11-30 | One-step method for synthesizing lactone type crown ether by lactone ring expansion |
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| CN101186604B true CN101186604B (en) | 2010-07-21 |
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| JP6710552B2 (en) * | 2015-03-20 | 2020-06-17 | 三洋化成工業株式会社 | Cyclic polyether ester, lubricating oil composition containing the same, and method for producing cyclic polyether ester |
| JP6783711B2 (en) * | 2016-08-04 | 2020-11-11 | 三洋化成工業株式会社 | Cleaning agent composition |
| JP6823567B2 (en) * | 2016-08-22 | 2021-02-03 | 三洋化成工業株式会社 | Antibacterial composition |
| JP6935281B2 (en) * | 2016-09-21 | 2021-09-15 | 三洋化成工業株式会社 | Adsorbent composition and method of adsorbing harmful substances using it |
| JP6730897B2 (en) * | 2016-09-26 | 2020-07-29 | 三洋化成工業株式会社 | Rotaxane |
| JP6921700B2 (en) * | 2016-09-29 | 2021-08-18 | 三洋化成工業株式会社 | Antistatic resin composition |
| JP6975037B2 (en) * | 2016-12-29 | 2021-12-01 | 三洋化成工業株式会社 | Cyclic polyether ester composition and its production method |
| JP7001518B2 (en) * | 2017-05-30 | 2022-02-15 | 三洋化成工業株式会社 | Cyclic compound composition and method for producing the same |
| JP7118817B2 (en) * | 2017-09-04 | 2022-08-16 | 三洋化成工業株式会社 | Cyclic polyester composition and method for producing the same |
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