CN116082155A - Method for preparing pinoxaden intermediate by using symmetrical epoxy compound - Google Patents

Method for preparing pinoxaden intermediate by using symmetrical epoxy compound Download PDF

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CN116082155A
CN116082155A CN202211691998.5A CN202211691998A CN116082155A CN 116082155 A CN116082155 A CN 116082155A CN 202211691998 A CN202211691998 A CN 202211691998A CN 116082155 A CN116082155 A CN 116082155A
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孙智华
陈思远
吴惠屹
杨希辰
郑慧贇
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Shanghai University of Engineering Science
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/313—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of doubly bound oxygen containing functional groups, e.g. carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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Abstract

The invention relates to a method for preparing pinoxaden intermediate by using symmetrical epoxy compounds, which comprises the following steps: (1) Grignard reagent of formula (2) and dialkyl epoxysuccinate of formula (3) to form compound of formula (4); or with epoxymaleic anhydride of formula (6) or epoxysuccinonitrile of formula (7) to produce a compound of formula (8) or formula (10); (2) Oxidizing the compound of formula (4) to form a compound of formula (5), or oxidizing the compound of formula (8) or formula (10) to form a compound of formula (9) or formula (11), and hydrolyzing to form a compound of formula (5); (3) The compound of formula (5) is heated to remove CO to produce the compound of formula (1). The method has the advantages of short synthesis steps, high yield of each step, avoidance of expensive transition metal and ligand, and industrialized production.

Description

Method for preparing pinoxaden intermediate by using symmetrical epoxy compound
Technical Field
The invention relates to the field of organic synthesis, in particular to a method for preparing pinoxaden intermediate by using symmetrical epoxy compounds.
Background
The pinoxaden is a phenyloxazoline herbicide developed by the company n-da, is an acetyl coenzyme A Acidylase (ACC) inhibitor and is mainly used for preventing and killing annual gramineous weeds in a barley field. In the process of preparing the pesticide, the compound (1) is a key intermediate for synthesizing pinoxaden, and the synthesis method of the compound (1) is mainly summarized in the following 4 methods.
Method 1: according to j.org.chem.2011,76,8107 report:
Figure SMS_1
the route is only of academic significance in terms of the yield of key steps, the synthesis steps, the use of transition noble metals and ligands, and the like, for preparing the compound (1) from the arylboronic acid.
Method 2: according to WO2013060744 it is reported that:
Figure SMS_2
the route starts from dibromo aromatic amine to prepare the compound (1), and has long synthesis steps, high economic cost and environment friendliness.
Method 3: according to Bioorganic & Medicinal Chemistry,2009,17 (12), 4241 reports:
Figure SMS_3
the route starts from diethyl phenol to prepare the compound (1), and has long synthesis steps and high economic cost.
Method 4: according to WO2000078881 it is reported that:
Figure SMS_4
the route starts from methyl diethyl aniline to prepare the compound (1), has short synthesis steps, relates to the use of transition metals, and has high cost.
Therefore, there is a need for improvements over the prior art, reducing costs and synthetic steps, and being environmentally friendly, capable of adapting to the needs of large-scale industrial production.
Disclosure of Invention
Aiming at the technical problems, the invention aims to provide a method for preparing pinoxaden intermediate by using symmetrical epoxy compounds.
The technical proposal is as follows: the structural general formula of the pinoxaden intermediate is shown as formula (1), wherein R is C1-C6 alkyl (straight chain or branched chain), phenyl, substituted phenyl or benzyl. Preferably C2-C6 alkyl, phenyl, pentafluorophenyl or benzyl, said symmetrical epoxy compound being a symmetrical 4 carbon containing epoxy compound selected from the group consisting of compounds of formula (3), formula (6) and formula (7);
the method comprises the following steps:
reacting (1) a Grignard reagent of formula (2) with an epoxysuccinic diester of formula (3), an epoxymaleic anhydride of formula (6) or an epoxysuccinonitrile of formula (7), respectively, to produce a compound of formula (4), formula (8) or formula (10); x in the formula (2) is Cl, br or I; r in the formula (3) is C1-C6 alkyl (straight chain or branched), phenyl, substituted phenyl or benzyl. Preferably C2-C6 alkyl, phenyl, pentafluorophenyl or benzyl;
(2) Oxidizing the compound of formula (4) to produce a compound of formula (5), or,
oxidizing the compound of formula (8) or (10) to form a compound of formula (9) or (11), and hydrolyzing to form a compound of formula (5);
(3) The compound of formula (5) is heated to remove CO to produce the compound of formula (1).
Figure SMS_5
The synthetic route is illustrated as follows:
Figure SMS_6
Figure SMS_7
specifically, in the step (1), the preparation method of the Grignard reagent comprises the steps of mixing magnesium and an initiator in a solvent, and adding 2, 6-diethyl-4-methyl halogenated benzene, wherein halogen elements on the 2, 6-diethyl-4-methyl halogenated benzene are Cl, br or I, and preferably Br.
The solvent is diethyl ether, tetrahydrofuran or dioxane; the initiator is at least one of iodine, DMF and dibromoethane, preferably iodine and dibromoethane. The molar ratio of the 2, 6-diethyl-4-methyl halogenated benzene to the magnesium to the iodine to the dibromoethane is 1:0.9-1.5:0.003-0.006:0.03-0.06.
The reaction is carried out at a temperature of 0 to 100℃and preferably at a temperature of 40 to 60 ℃.
Figure SMS_8
In the step (1), the molar ratio of the Grignard reagent to the symmetrical epoxy compound is 1:0.9-1.1, preferably 1:1, a step of; the reaction temperature is-80 to 20 ℃, preferably-5 to 5 ℃, and the corresponding ring-opening product compound of formula (4), (8) or (10) is obtained. In a preferred embodiment of the invention, the reaction temperature is 0 ℃. The solvent used for the reaction of the grignard reagent with the symmetrical epoxide is diethyl ether, tetrahydrofuran or dioxane.
After the reaction was completed, hydrochloric acid was added, the organic phase was separated, the aqueous phase was extracted with ethyl acetate, and the organic phases were combined for drying and purification.
Symmetrical epoxy compounds (3), (6) or (7) of 4 carbons can be prepared according to the methods of j.
Figure SMS_9
In the step (2), peroxide compound is used as oxidant for oxidation, and the peroxide compound comprises hydrogen peroxide, hypochlorous acid and NaOCl, KOCl, naClO 2 、NaBrO 2 、KClO 2 Swern oxidizing agent, m-chloroperoxybenzoic acid, peracetic acid, cr-based oxidizing agent (such as chromic acid-based compound, etc.), or Mn-based oxidizing agent (such as manganic acid or permanganic acid-based compound, etc.).
Figure SMS_10
The dosage ratio of the compound of formula (4), formula (8) or formula (10) to the oxidant is 1:2-3, preferably 1:2-2.5.
The step of oxidation reaction of the compound of formula (4) is: adding formula (4) into the mixture of organic solvent containing bicarbonate and water, and slowly adding peroxide until the reaction is complete. Preferably, tempo (tetramethylpiperidine oxide) is added as catalyst in a molar ratio to the compound of formula (4) of 1:10-40. The organic solvent is acetonitrile or tetrahydrofuran. Preferably, the peroxy compound is sodium hypochlorite or potassium hypochlorite.
The oxidation conditions of the compound of formula (8) or (10) are that the compound of formula (8) or (10) is mixed with an organic solvent, and an oxidant peroxy compound is added until the reaction is finished. Preferably, tempo (tetramethylpiperidine oxide) is added as catalyst in a molar ratio of 1 to the compound of formula (8) or (10): 10-40. The organic solvent is acetonitrile or tetrahydrofuran. Preferably, the peroxy compound is hydrogen peroxide.
After the oxidation reaction is finished, washing with water and dichloromethane, and taking an organic phase; the aqueous phase is extracted with dichloromethane and the organic phases are combined, washed, dried, the solvent is removed and purified to give the compound of formula (9) or (11).
In the step (2), the hydrolysis and esterification conditions of the compound of the formula (9) or the formula (11) are as follows: the reaction of the compounds of the formula (9) or (11) with C1-C6 alcohols, preferably C2-C6 alcohols, gives a phaseThe corresponding esters (compounds of formula (5)). Preferably, SOCl is added 2 And DMF as catalyst. After the reaction is finished, removing the solvent and purifying to obtain the compound of the formula (5).
Figure SMS_11
In the step (3), the reaction conditions for the pyrolysis of CO are as follows: the compound of formula (5) is mixed with anhydrous alcohol and pyrolyzed at 600-200 ℃. Preferably, the alcohol is a C1-C6 alcohol, more preferably a C2-C6 alcohol.
After the reaction is completed, the solvent is removed and purified to obtain the compound of formula (1).
The invention adopts bromobenzene Grignard reagent to react with epoxy compound with symmetrical structure of 4 carbons to form compound (4), (8) or (10), and then the target compound (1) is generated through oxidative decarboxylation reaction. The synthesis steps are short, the yield of each reaction step is high, the use of expensive transition metal and ligand is avoided, and the method has the advantage of industrial production.
Detailed Description
The technical features of the technical scheme provided by the invention are further clearly and completely described below by using 2 different symmetrical epoxy compounds with 4 carbons as raw materials and combining the specific embodiments, but the scope of the invention is not limited by the examples.
It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1 Synthesis of diethyl 2- (2, 6-diethyl-4-methylphenyl) -malonate (1) using diethyl epoxysuccinate
The first step: synthesis of 3- (2, 6-diethyl-4-methylphenyl) -4-hydroxy-butanedioic acid diethyl ester (4)
Figure SMS_12
Under the protection of nitrogen, 2.46 g (0.103 mol) of magnesium chips are added into 80 g of dry tetrahydrofuran, 0.11 g (0.0004 mol) of iodine and 0.88 g (0.0044 mol) of 1, 2-dibromoethane are added, the reaction solution is heated to 50 ℃,20 g (0.088 mol) of 2, 6-diethyl-4-methyl bromobenzene is slowly added into the reaction solution in a dropwise manner, the internal temperature is not more than 60 ℃, after the dropwise addition, the reaction solution is continuously reacted at 50 ℃ for 2 hours, and the reaction solution is cooled to room temperature. 16.5 g (0.088 mol) of compound (3) is dissolved in 100 g of tetrahydrofuran, the temperature is reduced to 0 ℃ and the prepared Grignard reagent is added into the reaction liquid under the protection of nitrogen, the reaction liquid is naturally cooled to room temperature after the completion of the dripping, the reaction liquid is continuously stirred for 12 hours until the raw materials disappear, then 100 ml of 1M hydrochloric acid is added, an organic phase is separated, the aqueous phase is extracted with 200 ml of ethyl acetate, the organic phases are combined, dried and purified, and 23 g of compound (4) is obtained, and the yield is 78%. 1 HNMR(400MHz,CDCl 3 )δppm:1.18(t,J＝7.5Hz,6H),1.23(q,J＝7.2Hz,6H)，1.28(q,J＝7.2Hz,6H)，2.30(s,3H),2.64(q,J＝7.5Hz,4H),4.13(t,J＝7.2Hz,4H),4.19(t,J＝7.2Hz,4H),3.24(d,J＝7.2Hz,1H),4.56(d,J＝7.2Hz,1H),6.93(s,2H).
And a second step of: synthesis of 3- (2, 6-diethyl-4-methylphenyl) -4-carbonyl-succinic acid diethyl ester (5)
Figure SMS_13
1.8 g of sodium bicarbonate was dissolved in 17.5 g of water, 20 g of acetonitrile was further added, 3.36 g (10 mmol) of compound (4) and 0.1 g (0.2 mmol) of TEMPO were added to the above solution, cooled to 0℃and 0.14 g (0.2 mmol) of an 11% aqueous solution of sodium hypochlorite was slowly added dropwise for 30 minutes, under this reaction condition, 2.4 g (21 mmol) of an aqueous solution of sodium hypochlorite was continuously added again, the reaction was detected to be completed, 100 ml of water and 200 ml of dichloromethane were added, the organic phase was separated, the aqueous phase was once extracted with dichloromethane again, the organic phase was combined, washed with water, dried, the solvent was recovered under reduced pressure, and silica gel was separated and purified to obtain 3 g of compound (5) in a yield of 90%.
1 HNMR(400MHz,CDCl 3 )δppm:1.18(t,J＝7.5Hz,6H),1.23(q,J＝7.2Hz,6H)，1.28(q,J＝7.2Hz,6H)，2.30(s,3H),2.64(q,J＝7.5Hz,4H),4.13(t,J＝7.2Hz,4H),4.19(t,J＝7.2Hz,4H),5.08(s,1H),6.93(s,2H).
And a third step of: synthesis of diethyl 2- (2, 6-diethyl-4-methylphenyl) -malonate (1)
Figure SMS_14
To 100 ml of absolute ethanol, 3.34 g of compound (5) was added, and after heating to 80℃for 1 hour, the reaction was checked for completion, the solvent was recovered under reduced pressure, and silica gel was separated and purified to obtain 2.54 g of compound (1) in 83% yield. 1 HNMR(400MHz,CDCl 3 )δppm:1.18(t,J＝7.5Hz,6H),1.23(q,J＝7.2Hz,6H)，2.30(s,3H),2.64(q,J＝7.5Hz,4H),4.13(t,J＝7.2Hz,4H),5.06(s,1H),6.93(s,2H).
EXAMPLE 2 Synthesis of diethyl 2- (2, 6-diethyl-4-methylphenyl) -malonate (1) using epoxydihydro-maleic anhydride
The first step: synthesis of 3- (2, 6-diethyl-4-methylphenyl) -4-hydroxy-dihydro-maleic anhydride (8)
Figure SMS_15
Under the protection of nitrogen, 2.46 g (0.088 mol) of magnesium turnings are added into 80 g of dry tetrahydrofuran, 0.11 g (0.0004 mol) of iodine and 0.88 g (0.0044 mol) of 1, 2-dibromoethane are added, the reaction solution is heated to 50 ℃,20 g (0.088 mol) of 2, 6-diethyl-4-methyl bromobenzene is slowly added into the reaction solution in a dropwise manner, the internal temperature is not more than 60 ℃, after the dropwise addition, the reaction solution is continuously reacted at 50 ℃ for 2 hours, and the reaction solution is cooled to room temperature. 10 g (0.088 mol) of compound (6) is dissolved in 100 g of tetrahydrofuran, the temperature is reduced to 0 ℃, the prepared Grignard reagent is dripped into the reaction liquid under the protection of nitrogen, the reaction liquid is naturally cooled to room temperature after dripping, stirring is continued for 12 hours until the raw materials disappear, then 100 ml of 1M hydrochloric acid is added, an organic phase is separated, the aqueous phase is extracted with 200 ml of ethyl acetate, the organic phases are combined, dried and purified, and 16 g of compound (8) is obtained, and the yield is 72%.
1 HNMR(400MHz,CDCl 3 )δppm:1.19(t,J＝7.5Hz,6H),2.33(s,3H),2.66(q,J＝7.5Hz,4H),3.56(d,J＝7.2Hz,1H),4.36(d,J＝7.2Hz,1H),6.95(s,2H).
And a second step of: synthesis of 3- (2, 6-diethyl-4-methylphenyl) -4-carbonyl-dihydro-maleic anhydride (9)
Figure SMS_16
In 50 ml of acetonitrile, 2.62 g (10 mmol) of compound (8) and 0.1 g (0.2 mmol) of TEMPO are cooled to 0 ℃,2 g (40 mmol) of 35% hydrogen peroxide solution is slowly added dropwise for 30 minutes, 100 ml of water and 200 ml of dichloromethane are added to detect the end of the reaction, an organic phase is separated, the aqueous phase is extracted once with dichloromethane, the organic phases are combined, washed with water, dried, the solvent is recovered under reduced pressure, and silica gel is separated and purified to obtain 2.3 g of compound (9) with a yield of 88%.
1 HNMR(400MHz,CDCl 3 )δppm:1.19(t,J＝7.5Hz,6H),2.33(s,3H),2.66(q,J＝7.5Hz,4H),5.16(s,1H),6.95(s,2H).
And a third step of: synthesis of 2- (2, 6-diethyl-4-methylphenyl) -malonic acid (5)
Figure SMS_17
To 30 ml of absolute ethanol, 2.6 g (10 mmol) of compound (9) and a drop of DMF were added, the reaction solution was cooled to 0℃and 1.2 g (10 mmol) of thionyl chloride was added dropwise, the reaction was naturally warmed to room temperature, the reaction was carried out for 10 hours, the reaction was completed, the solvent was recovered under reduced pressure, and silica gel was separated and purified to give 2.8 g of a pale oily compound (5) in 92% yield.
1 HNMR(400MHz,CDCl 3 )δppm:1.18(t,J＝7.5Hz,6H),1.23(q,J＝7.2Hz,6H)，2.30(s,3H),2.64(q,J＝7.5Hz,4H),4.13(t,J＝7.2Hz,4H),5.06(s,1H),6.93(s,2H).
Fourth step: synthesis of diethyl 2- (2, 6-diethyl-4-methylphenyl) -malonate (1)
The synthesis method of this step is the same as that of the third step in example 1.
Example 3
Synthesis of 8- (2, 6-diethyl-4-methylphenyl) tetrahydropyrrole [1,2-d ] [1,4,5] oxadiazepine-7, 9-dione heptane (13)
Figure SMS_18
30.6 g (0.1 mol) of diethyl 2- (2, 6-diethyl-4-methylphenyl) maleate are dissolved in 200 ml of xylene, 19 g (0.11 mol) of 1,4, 5-oxydiazepane dihydrochloride are added at room temperature, 22 g (0.21 mol) of triethylamine are heated to 60℃and reacted for 1 hour, after 1,4, 5-oxydiazepane is converted to the free state, the reaction is further heated to reflux, the ethanol produced by the reaction can be removed in the middle, the reaction is no longer produced until the ethanol is produced, approximately the reflux (removal of the alcohol) is required for 5 hours, the reaction is finished, cooled to room temperature, triethylamine hydrochloride is filtered off, xylene is recovered, the crude product is purified by sodium salt reprecipitation, hydrochloric acid conditioning recovery is carried out, specifically by adding 300 ml of 1N sodium hydroxide solution, dissolving the crude product, washing 2 times with dichloromethane (discarding), the alkaline aqueous solution is adjusted to pH 2-3 with 4N brine, white solid is precipitated, 29 g of white powder is obtained after drying, purity is 98%).
1 H NMR(CDCl 3 ):δ2.06(s,3H),2.25(s,3H),2.39(s,3H),3.81(ddd,2H),3.92–4.02(m,4H),4.22(ddd,2H),4.72(s,1H),6.83(s,1H),6.93(s,1H). 13 C NMR(CDCl 3 ):δ20.0,20.9,21.0,46.1,48.3,70.5,125.9,129.5,130.0,136.1,138.2,138.4,165.5.MS(ES + )m/z:289(C16H20N2O3+H) + .
2. Synthesis of pinoxaden (14)
Figure SMS_19
Under the protection of nitrogen, 20 g of 8- (2, 6-diethyl-4-methylphenyl) tetrahydropyrrole [1,2-d ] [1,4,5] oxydiaza-7, 9-dione heptane is dissolved in 200 ml of dry tetrahydrofuran, cooled to 20 ℃, 16 g of triethylamine and 0.2 g of 4-dimethylaminopyridine are added under stirring, 50 g of pivaloyl chloride is dropwise added, the reaction temperature is kept at 20-25 ℃ until the reaction is finished, the reaction solution is washed with 20% of saline, the organic phase is dried and concentrated, the crude product is recrystallized in methyl tertiary butyl ether, and the dried product is obtained, wherein 19 g of pinoxaden with the purity of 98.1% and the yield is 75%. Mp:122-123 ℃.
1 H NMR(CDCl 3 ):δ1.03(s,9H),1.12(t,6H),2.29(s,3H),2.35-2.63(m,4H),3.81-3.90(m,4H),3.93(m,2H),4.26(m,2H),6.88(s,2H). 13 C NMR(CDCl 3 ):δ14.7,21.3,26.3,26.4,39.1,45.6,49.5,69.4,70.6,97.3,122.7,126.0,137.7,144.3,149.1,162.0,174.1.FD-MS m/z:400(C23H32N2O4) + .HRMS(EI+)m/z:Calcd for(C23H32N2O4) + :400.2362；Found:400.2361.

Claims (6)

1. A method for preparing pinoxaden intermediate by using symmetrical epoxy compound is characterized in that the structural general formula of the pinoxaden intermediate is shown as a formula (1), wherein R is C1-C6 alkyl, phenyl, substituted phenyl or benzyl, and the symmetrical epoxy compound is selected from compounds shown as a formula (3), a formula (6) or a formula (7); the method comprises the following steps:
Figure FDA0004021397390000011
(1) Grignard reagent of formula (2) and epoxysuccinic diester of formula (3) to form a compound of formula (4); or alternatively
Reacting with an epoxymaleic anhydride of formula (6) or epoxysuccinonitrile of formula (7) to produce a compound of formula (8) or formula (10); x in the formula (2) is Cl, br or I; r in formula (3) is wherein R is C1-C6 alkyl, phenyl, substituted phenyl or benzyl;
(2) Oxidizing the compound of formula (4) to produce a compound of formula (5), or,
oxidizing the compound of formula (8) or (10) to form a compound of formula (9) or (11), and hydrolyzing to form a compound of formula (5);
(3) The compound of formula (5) is heated to remove CO to produce the compound of formula (1).
2. The method according to claim 1, wherein in the step (1), the molar ratio of the grignard reagent to the symmetrical epoxy compound is 1:0.9-1.1; the reaction temperature is-80-20 ℃.
3. The method according to claim 1, wherein in the step (2), the oxidation is performed using a peroxide compound as an oxidizing agent, the peroxide compound comprising hydrogen peroxide, hypochlorous acid, naOCl, KOCl, naClO 2 、NaBrO 2 、KClO 2 Swern oxidant, m-chloroperoxybenzoic acid, peracetic acid, cr-based oxidant or Mn-based oxidant.
4. The process according to claim 1, wherein in step (2), the ratio of the compound of formula (4), formula (8) or formula (10) to the amount of oxidizing agent is 1:2-3, adding tetramethyl piperidine oxide as a catalyst.
5. The process of claim 1, wherein in step (3), the compound of formula (9) or (11) is reacted with a C1-C6 alcohol to form the corresponding ester.
6. The process according to claim 1, wherein in step (3), the reaction conditions for the thermal decomposition of CO are: the compound of formula (5) is mixed with an anhydrous alcohol, and pyrolyzed at 600-200 ℃, wherein the alcohol is C1-C6 alcohol.
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Citations (5)

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