Production process of sex attractant (R, Z)-5-(1-decene) dihydrofuran-2 (3H)-ketone of Japanese ponceau

Abstract

The invention relates to a production process of (R, Z)-5-(1-decene) dihydrofuran-2 (3H)-ketone serving as a sex attractant of Japanese turtles, which comprises the following steps: (1) reacting 1-bromononane serving as a raw material with triphenylphosphine at a certain temperature and under the condition of a solvent to prepare nonyl triphenyl phosphorus bromide as shown in a formula (II); (2) taking 4-pentenoic acid as a raw material, and carrying out oxidation reaction and intramolecular esterification reaction in the presence of an oxidizing agent to prepare a target fragment (R)-5-hydroxymethyl dihydrofuran-2-one shown as a formula (III); (3) taking the (R)-5-hydroxymethyl dihydrofuran-2-ketone shown in the formula (III) as a raw material, and carrying out oxidation reaction to prepare a target fragment (R)-5-oxotetrahydrofuran-2-formaldehyde shown in the formula (IV); and (4) carrying out Wittig reaction on (R)-5-oxotetrahydrofuran-2-formaldehyde as shown in the formula (IV) and nonyltriphenylphosphorus bromide as shown in the formula (II) in the presence of alkali to prepare the (R, Z)-5-(1-decene) dihydrofuran-2 (3H)-ketone as shown in the formula (I). The method has the advantages of short reaction route, cheap and easily available raw materials, mild reaction conditions, easy amplification, small environmental pollution, and good economic and social values in popularization.

Description

Technical Field

[0001] The invention belongs to the field of chemical synthesis and relates to a production process of a Japanese beetle sex attractant (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one. Background Art

[0002] The Japanese beetle, scientifically known as Popillia japonica Newman, belongs to the family Albiziaceae. It is a polyphagous pest that hosts nearly 300 species of plants. The beetle is widely distributed around the world and is an important pest in agriculture, forestry and animal husbandry. The adult feeds on the flowers, fruits and leaves of plants, while the larvae (grubs) damage the roots and stems of plants, resulting in a large-scale reduction in crop yields and the loss of commercial value of flowers and fruits.

[0003] Traditional chemical control and biological control are difficult to achieve ideal results. For example, the United States has used methods such as spraying poisons and introducing natural enemies to prevent its spread, but has not achieved significant results. Compared with traditional methods, sex attractant control has the advantages of high selectivity, high efficiency, non-toxicity, and environmental friendliness. In 1976, Tumlinson et al. confirmed that the sex pheromone of the female Japanese beetle is (R,Z)-5-(1-decene)dihydrofuran-2(3H)-one.

[0004] (R,Z)-5-(1-decene)dihydrofuran-2(3H)-one, the structural formula of which is shown in formula (I):

[0005] Formula (I):

[0006] At present, the methods reported for synthesizing (R,Z)-5-(1-decene)dihydrofuran-2(3H)-one are mainly as follows:

[0007] (1) In 1983, Shuji Senda et al. prepared the Japanese beetle sex attractant (R,Z)-5-(1-decene)dihydrofuran-2(3H)-one using dec-1-ynyl(trimethyl)silane and succinic acid monomethyl chloride as raw materials.

[0008] The disadvantages of this route are: the reduction reaction requires LiAlH4, which is very active and may be dangerous if not handled properly; the reaction must be carried out at a low temperature of -100℃ to -65℃, which places extremely high demands on equipment and operation.

[0009] (2) In 1992, Takashi Ebata et al. used D-ribose as the starting material to prepare the Japanese scarab beetle sex attractant (R,Z)-5-(1-decene)dihydrofuran-2(3H)-one.

[0010] The disadvantages of this route are: in the process of preparing 1,2-epoxy-3,4-(isopropylenedioxy)-5-dodecane, sodium hydride treatment is required, which is relatively dangerous; the overall experimental conditions are relatively high and cannot meet the requirements of large-scale production.

[0011] (3) From 1995 to 1997, Xu Zhanghuang et al. prepared the Japanese scarab beetle sex attractant (R,Z)-5-(1-decenyl)dihydrofuran-2(3H)-one using γ-butyrolactone and succinic anhydride as raw materials.

[0012] The disadvantages of this route are: the use of alkenyl copper lithium reagents, the preparation process of copper lithium reagents is complicated, special chemical treatment is required and it is difficult to preserve after preparation, and it cannot meet the requirements of large-scale production.

[0013] (4) In 1996, Xu Zhanghuang et al. used propargyl alcohol as raw material to prepare the Japanese scarab beetle sex attractant (R,Z)-5-(1-decenyl)dihydrofuran-2(3H)-one.

[0014] The disadvantages of this route are: it includes the steps of functional group protection, Grignard exchange and Grignard coupling, deprotection oxidation, nucleophilic addition, ring closure reaction, oxidation of secondary alcohol to lactone, selective catalysis, etc. The synthetic route is long, and the multi-step Grignard reaction has high requirements for reaction conditions and is somewhat dangerous.

[0015] (5) In 2007, Gowravaram Sabitha et al. used 4-pentanol as the starting material and adopted an asymmetric synthesis strategy to prepare the Japanese scarab beetle sex attractant (R,Z)-5-(1-decenyl)dihydrofuran-2(3H)-one.

[0016] The disadvantages of this route are that metallic lithium is used in the base-induced ring opening, which is active in nature and requires special care in its storage and use. At the same time, the synthesis method has 12 steps, a long reaction route, harsh reaction conditions, and a low overall yield.

[0017] (6) In 2014, Hao Xu et al. used Zn-ProPhenol and Brown's P2-Ni catalysts to prepare the Japanese beetle sex attractant (R,Z)-5-(1-decene)dihydrofuran-2(3H)-one by asymmetric addition of methyl propionate to 2-undecyne-1-aldehyde and selective partial reduction of diynol esters.

[0018] Disadvantages of this route: Two expensive catalysts are used, and the reaction conditions are variable and complex. The reaction route is long, the overall yield is low, and it is difficult to industrialize. Summary of the invention

[0019] In view of the above technical status, the present invention provides a safe and reliable production process of the Japanese beetle sex attractant (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one, which has a short route, generates less waste, has low cost, and has high yield and selectivity.

[0020] The technical solution of the present invention can be summarized as follows:

[0021] The production process of (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one, wherein the (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one has a structure shown in formula (I):

[0022] Formula (I):

[0023] The steps include:

[0024] (1) Using 1-bromononane as a raw material, reacting with triphenylphosphine under certain temperature and solvent conditions to obtain nonyltriphenylphosphonium bromide (II);

[0025] (2) using 4-pentenoic acid as a raw material, an oxidation reaction and an intramolecular esterification reaction are carried out in the presence of an oxidant to obtain the target fragment (R)-5-hydroxymethyldihydrofuran-2-one (III);

[0026] (3) using (R)-5-hydroxymethyldihydrofuran-2-one (III) as a raw material, adding an oxidant and a desiccant, and obtaining the target fragment (R)-5-oxotetrahydrofuran-2-carboxaldehyde (IV) through an oxidation reaction;

[0027] (4) Using (R)-5-oxotetrahydrofuran-2-carboxaldehyde (IV) as a raw material and nonyltriphenylphosphonium bromide (II) in the presence of a base, a Wittig reaction is carried out to obtain the target product, Japanese beetle sex attractant (R,Z)-5-(1-decene)dihydrofuran-2(3H)-one (I).

[0028] According to the present invention, preferably, the nonyltriphenylphosphonium bromide in step (1) has a structure shown in formula (II):

[0029] Formula (II):

[0030] According to the present invention, preferably, the reaction in step (1) is carried out in a solvent, and further preferably, the solvent is one or a combination of N,N-dimethylformamide, N,N-dimethylacetamide, toluene, acetonitrile, and xylene;

[0031] Preferably, the temperature in step (1) is controlled at 70°C to 150°C;

[0032] Preferably, the molar ratio of 1-halononane to triphenylphosphine in the reaction in step (1) is 1:(1-4).

[0033] According to the present invention, preferably, the (R)-5-hydroxymethyldihydrofuran-2-one in step (2) has a structure shown in formula (III):

[0034] Formula (III):

[0035] Preferably, in step (2), the oxidant is one or a combination of performic acid, peracetic acid, perpropionic acid, perbenzoic acid, meta-chloroperbenzoic acid, trifluoroperacetic acid, formic acid and hydrogen peroxide, acetic acid and hydrogen peroxide, acetic anhydride and hydrogen peroxide, potassium permanganate, and osmium tetroxide;

[0036] Preferably, in step (2), the molar ratio of the raw material 4-pentenoic acid to the oxidant is 1:(1.1-3);

[0037] Preferably, the reaction temperature of step (2) is controlled at 20°C to 70°C.

[0038] According to the present invention, preferably, the (R)-5-oxotetrahydrofuran-2-carboxaldehyde in step (3) has a structure shown in formula (IV):

[0039] Formula (IV):

[0040] According to the present invention, preferably, the oxidant in the reaction in step (3) is one or a combination of Dess-Martin oxidant, pyridinium dichromate, chromic acid, pyridinium chlorochromate, pyridinium fluorochromate, and potassium permanganate;

[0041] Preferably, in step (3), the molar ratio of the raw material (R)-5-hydroxymethyldihydrofuran-2-one to the oxidant is 1:(1-4);

[0042] Preferably, the reaction temperature of step (3) is controlled at 10°C to 40°C;

[0043] Preferably, the desiccant in step (3) is one or a combination of anhydrous magnesium sulfate, silica gel powder, and molecular sieve.

[0044] According to the present invention, preferably, the (R,Z)-5-(1-decene)dihydrofuran-2(3H)-one in step (4) has a structure shown in formula (I):

[0045] Formula (I):

[0046] According to the present invention, preferably, the reaction in step (4) is carried out in a solvent, and further preferably, the solvent is one or a combination of tetrahydrofuran, toluene, N,N-dimethylformamide, and diethyl ether;

[0047] Preferably, in step (4), the base is one or a combination of potassium bis(trimethylsilyl)amide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, trityl sodium, sodium amide, potassium tert-butoxide, lithium diisopropylamide, potassium carbonate, potassium hydroxide, and sodium hydroxide;

[0048] Preferably, in step (4), the molar ratio of the raw material (R)-5-oxotetrahydrofuran-2-carbaldehyde to the base is 1:(1.1-2.0);

[0049] Preferably, the reaction temperature of step (4) is controlled at -40°C to 30°C;

[0050] Preferably, the reaction in step (4) is carried out under a nitrogen atmosphere.

[0051] The beneficial effects of the present invention are as follows:

[0052] The invention innovatively uses 4-pentenoic acid as the starting material, and only needs 4 steps of reaction to obtain the target product with a high yield. The synthetic route is short, the reaction conditions are mild, the raw material price is low, the environmental pollution is small, the operation is simple, and it is suitable for large-scale industrial production. DETAILED DESCRIPTION

[0053] The invention provides a production process of (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one which has a short route, is safe and reliable, generates less waste, has low cost, and has high yield and selectivity.

[0054] The preparation route of the Japanese scarab beetle sex attractant (R,Z)-5-(1-decene)dihydrofuran-2(3H)-one of the present invention is as follows:

[0055]

[0056] A method for preparing (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one, wherein the (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one has a structure shown in formula (I):

[0057] Formula (I):

[0058] The steps include:

[0059] (1) Using 1-bromononane as a raw material, reacting with triphenylphosphine under certain temperature and solvent conditions to obtain nonyltriphenylphosphonium bromide (II);

[0060] (2) using 4-pentenoic acid as a raw material, an oxidation reaction and an intramolecular esterification reaction are carried out in the presence of an oxidant to obtain the target fragment (R)-5-hydroxymethyldihydrofuran-2-one (III);

[0061] (3) using (R)-5-hydroxymethyldihydrofuran-2-one (III) as a raw material, adding an oxidant and a desiccant, and obtaining the target fragment (R)-5-oxotetrahydrofuran-2-carboxaldehyde (IV) through an oxidation reaction;

[0062] (4) Using (R)-5-oxotetrahydrofuran-2-carboxaldehyde (IV) as a raw material and nonyltriphenylphosphonium bromide (II) in the presence of a base, a Wittig reaction is carried out to obtain the target product, Japanese beetle sex attractant (R,Z)-5-(1-decene)dihydrofuran-2(3H)-one (I).

[0063] According to the present invention, in one or more preferred embodiments, the nonyltriphenylphosphonium bromide in step (1) has a structure shown in formula (II):

[0064] Formula (II):

[0065] In one or more preferred embodiments, the reaction in step (1) is carried out in a solvent, and further preferably, the solvent is one or a combination of N,N-dimethylformamide, N,N-dimethylacetamide, toluene, acetonitrile, and xylene;

[0066] Preferably, the temperature in step (1) is controlled at 70°C to 150°C;

[0067] Preferably, in step (1), the molar ratio of 1-halononane to triphenylphosphine is 1:(1-4).

[0068] According to the present invention, in one or more preferred embodiments, in step (1), 1-bromononane is added to a three-necked flask, toluene is added, stirring is started, and then triphenylphosphine is added, the temperature is raised to 110° C., and maintained for 20 hours. The solid is cooled to precipitate, and the solid is washed with ethyl acetate, pulped, filtered, and then concentrated by rotary evaporation to obtain nonyltriphenylphosphonium bromide (II).

[0069] According to the present invention, in one or more preferred embodiments, the (R)-5-hydroxymethyldihydrofuran-2-one in step (2) has a structure shown in formula (III):

[0070] Formula (III):

[0071] In one or more preferred embodiments, the oxidant in the reaction in step (2) is one or a combination of performic acid, peracetic acid, perpropionic acid, perbenzoic acid, meta-chloroperbenzoic acid, trifluoroperacetic acid, formic acid and hydrogen peroxide, acetic acid and hydrogen peroxide, acetic anhydride and hydrogen peroxide, potassium permanganate, and osmium tetroxide;

[0072] Preferably, in step (2), the molar ratio of the raw material 4-pentenoic acid to the oxidant is 1:(1.1-3);

[0073] Preferably, the reaction temperature of step (2) is controlled at 20°C to 70°C.

[0074] According to the present invention, in one or more preferred embodiments, in step (2), peroxy acid is added to the reaction bottle, the temperature is raised to a certain temperature, 4-pentenoic acid is slowly added dropwise, and the temperature is maintained for a certain period of time after the addition is completed. The reaction is concentrated by rotary evaporation, and then methanol and 35% concentrated hydrochloric acid are added, and the temperature is maintained for a period of time. The solvent is removed by rotary evaporation to obtain (R)-5-hydroxymethyldihydrofuran-2-one (III).

[0075] According to the present invention, in one or more preferred embodiments, the (R)-5-oxotetrahydrofuran-2-carboxaldehyde in step (3) has a structure shown in formula (IV):

[0076] Formula (IV):

[0077] In one or more preferred embodiments, the oxidant in the reaction in step (3) is one or a combination of Dess-Martin oxidant, pyridinium dichromate, chromic acid, pyridinium chlorochromate, pyridinium fluorochromate, and potassium permanganate;

[0078] Preferably, in the reaction in step (3), the molar ratio of the raw material (R)-5-hydroxymethyldihydrofuran-2-one to the oxidant is 1:(1-4);

[0079] Preferably, the reaction temperature of step (3) is controlled at 10°C to 40°C;

[0080] Preferably, the desiccant in step (3) is one or a combination of anhydrous magnesium sulfate, silica gel powder, and molecular sieve.

[0081] According to the present invention, in one or more preferred embodiments, in step (3), (R)-5-hydroxymethyldihydrofuran-2-one is added to a reaction bottle, anhydrous dichloromethane is added, stirring is started, and a certain temperature is controlled. Then, an oxidant and a desiccant are added to the system, and the temperature is maintained and stirred for a certain time. Celite is spread and filtered, and the filtered mother liquor is directly concentrated and dried by rotary evaporation to obtain a crude product (R)-5-oxotetrahydrofuran-2-carboxaldehyde formula (IV).

[0082] According to the present invention, in one or more preferred embodiments, the (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one in step (4) has a structure shown in formula (I):

[0083] Formula (I):

[0084] In one or more preferred embodiments, the reaction in step (1) is carried out in a solvent, and further preferably, the solvent is one or a combination of tetrahydrofuran, toluene, N,N-dimethylformamide, and diethyl ether;

[0085] Preferably, in step (4), the base in the reaction is one or a combination of potassium bis(trimethylsilyl)amide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, trityl sodium, sodium amide, potassium tert-butoxide, lithium diisopropylamide, potassium carbonate, potassium hydroxide, and sodium hydroxide;

[0086] Preferably, in the step (4), the molar ratio of the raw material (R)-5-oxotetrahydrofuran-2-carbaldehyde to the base in the reaction is 1:(1.1-2.0);

[0087] Preferably, in step (4), the reaction temperature is controlled at -40°C to 30°C;

[0088] Preferably, in step (4), the reaction is carried out under a nitrogen atmosphere.

[0089] According to the present invention, in one or more preferred embodiments, in step (4), nonyltriphenylphosphonium bromide is added to the reaction bottle, an anhydrous solvent is added, stirring is started, the temperature is controlled, the nitrogen is replaced and the nitrogen protection system is protected. Add alkali to the system in 3 times, then heat up and maintain for a certain time. Then cool the system, slowly drop a mixture of (R)-5-oxotetrahydrofuran-2-carboxaldehyde crude product and solvent, and keep for a certain time after the dropwise addition. Then add water and dichloromethane to extract, dry the organic phase with anhydrous sodium sulfate, concentrate by rotary evaporation, and obtain (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one formula (I) after silica gel column chromatography.

[0090] In order to enable those skilled in the art to better understand the technical solution of the present invention, the present invention is further described in detail below in conjunction with specific implementation methods.

[0091] Example 1

[0092] The production process of (R,Z)-5-(1-decene)dihydrofuran-2(3H)-one comprises the following steps:

[0093] (1) Preparation of nonyltriphenylphosphonium bromide Formula (II):

[0094] 1-Bromononane (62.1 g, 0.3 mol) was added to a 1L three-necked flask, 500 ml of toluene was added, stirring was started, and then triphenylphosphine (118 g, 0.45 mol) was added, the temperature was raised to 110°C, and maintained for 20 hours. The solid was precipitated by cooling, and the solid was washed with ethyl acetate, pulped, filtered, and then concentrated by rotary evaporation and dried to obtain nonyltriphenylphosphonium bromide (II), an off-white solid (124 g), with a yield of 88.1%.

[0095] (2) Preparation of (R)-5-hydroxymethyldihydrofuran-2-one Formula (III):

[0096] Add formic acid (37g, 0.8mol) to a 500ml reaction bottle, then add 30% hydrogen peroxide (35g, 0.31mol) and raise the temperature to 50°C, start to slowly drop 4-pentenoic acid (21g, 0.21mol), add it in 1h, and then keep the temperature for 6h. Concentrate it by rotary evaporation, then add 80ml of methanol and 2.5g of 35% concentrated hydrochloric acid, control the temperature at 30°C, and keep it for 4h. Concentrate it by rotary evaporation to remove the solvent, and obtain (R)-5-hydroxymethyldihydrofuran-2-one formula (III), 23g of light yellow liquid, yield 94%, gas phase purity 95%.

[0097] (3) Preparation of (R)-5-oxotetrahydrofuran-2-carboxaldehyde Formula (IV):

[0098] Add (R)-5-hydroxymethyldihydrofuran-2-one (23g, 0.2mol) to a 500ml reaction bottle, add 200ml of anhydrous dichloromethane, start stirring, and control the temperature at 25°C. Then add pyridinium chlorochromate (64.6g, 0.3mol) and molecular sieves (64g) to the system twice, keep the temperature and stir for 4h. Filter with diatomaceous earth, and directly concentrate the filtered mother liquor by rotary evaporation to dryness to obtain crude (R)-5-oxotetrahydrofuran-2-carboxaldehyde (IV).

[0099] (4) Preparation of (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one Formula (I):

[0100] Add nonyltriphenylphosphonium bromide (122g, 0.26mol) to a 1L reaction bottle, add 500ml of anhydrous tetrahydrofuran, start stirring, control the temperature at -15℃, replace with nitrogen and protect the system with nitrogen. Add bis(trimethylsilyl)potassium amide (62g, 0.31mol) to the system in three times, then raise the temperature to 20℃ and keep for 1h. Then cool the system to -30℃, slowly drop a mixture of (R)-5-oxotetrahydrofuran-2-carboxaldehyde crude product and 50ml of tetrahydrofuran, and keep for 30min after the addition is complete. Add water and dichloromethane to extract, dry the organic phase with anhydrous sodium sulfate, concentrate by rotary evaporation, and obtain (R,Z)-5-(1-decene)dihydrofuran-2(3H)-one formula (Ⅰ) after silica gel column chromatography, 37.1g of colorless liquid, 88% yield of two-step reaction, and 98.5% purity.

[0101] 1 H NMR(300MHz, CDCl3)δ:0.88(t,J=6.9Hz,3H),1.27–1.40(m,12H),1.91–1.98(m,1H),2.06–2.16(m,2H),2.35–2.4 3(m,1H),2.53–2.59(m,2H),5.21–5.29(m,1H),5.42–5.49(m,1H),5.63–5.72(m,1H); (m,1H),5.63–5.72(m,1H).

[0102] Example 2

[0103] The production process of (R,Z)-5-(1-decene)dihydrofuran-2(3H)-one comprises the following steps:

[0104] (1) Preparation of nonyltriphenylphosphonium bromide Formula (II):

[0105] Add 1-bromononane (62.1 g, 0.3 mol) to a 1L three-necked flask, add 500 ml of N,N-dimethylformamide, start stirring, then add triphenylphosphine (157 g, 0.6 mol), raise the temperature to 90°C, and maintain for 15 hours, cool down and then evaporate to remove the solvent. Wash with ethyl acetate, pulp, filter, then evaporate and dry to obtain nonyltriphenylphosphonium bromide (II), off-white solid (130 g), yield 92.4%.

[0106] (2) Preparation of (R)-5-hydroxymethyldihydrofuran-2-one Formula (III):

[0107] Add acetic acid (64g, 0.8mol) to a 500ml reaction bottle, then add 30% hydrogen peroxide (79g, 0.7mol) and raise the temperature to 60°C, start to slowly drop 4-pentenoic acid (21g, 0.21mol), add it in 1h, and then keep the temperature for 4h. Concentrate it by rotary evaporation, then add 80ml of methanol and 2.5g of 35% concentrated hydrochloric acid, control the temperature at 30°C, and keep it for 4h. Concentrate it by rotary evaporation to remove the solvent, and obtain (R)-5-hydroxymethyldihydrofuran-2-one formula (III), 22.5g of light yellow liquid, with a yield of 92.4% and a gas phase purity of 96%.

[0108] (3) Preparation of (R)-5-oxotetrahydrofuran-2-carboxaldehyde Formula (IV):

[0109] Add Dess-Martin periodinane (148 g, 0.35 mol) and anhydrous magnesium sulfate 70 g into a 1L reaction bottle, add anhydrous dichloromethane 400 ml, start stirring, add pyridine (31.6 g, 0.4 mol), and control the temperature at 15°C. Then add (R)-5-hydroxymethyldihydrofuran-2-one (22.5 g, 0.19 mol) dropwise, and keep the temperature for 3 hours. Filter with diatomaceous earth, and directly concentrate the filtered mother liquor by rotary evaporation to dryness to obtain a crude product (R)-5-oxotetrahydrofuran-2-carboxaldehyde (IV).

[0110] (4) Preparation of (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one Formula (I):

[0111] Add nonyltriphenylphosphonium bromide (122g, 0.26mol) to a 1L reaction bottle, add 500ml of anhydrous tetrahydrofuran, start stirring, control the temperature at -25℃, replace and protect the system with nitrogen. Add trityl sodium (90g, 0.34mol) to the system in 3 times, then raise the temperature to 20℃ and keep it for 1h. Then cool the system to -20℃, slowly drop a mixture of (R)-5-oxotetrahydrofuran-2-carboxaldehyde crude product and 50ml of tetrahydrofuran, and keep it for 30min after the addition is complete. Add water and dichloromethane to extract, dry the organic phase with anhydrous sodium sulfate, concentrate by rotary evaporation, and obtain (R,Z)-5-(1-decene)dihydrofuran-2(3H)-one formula (Ⅰ) after silica gel column chromatography, 37.1g of colorless liquid, 89% yield of two-step reaction, and 98.7% purity.

[0112] 1H NMR(300MHz, CDCl3)δ:0.88(t,J=6.9Hz,3H),1.27–1.40(m,12H),1.91–1.98(m,1H),2.06–2.16(m,2H),2.35–2.4 3(m,1H),2.53–2.59(m,2H),5.21–5.29(m,1H),5.42–5.49(m,1H),5.63–5.72(m,1H); (m,1H),5.63–5.72(m,1H).

[0113] Example 3

[0114] The production process of (R,Z)-5-(1-decene)dihydrofuran-2(3H)-one comprises the following steps:

[0115] (1) Preparation of nonyltriphenylphosphonium bromide Formula (II):

[0116] 1-Bromononane (62.1 g, 0.3 mol) was added to a 1L three-necked flask, 500 ml of xylene was added, stirring was started, and then triphenylphosphine (235 g, 0.9 mol) was added, the temperature was raised to 130°C, and maintained for 12 hours, and the solvent was removed by rotary evaporation after cooling. It was washed with ethyl acetate, pulped, filtered, and then rotary evaporated and dried to obtain nonyltriphenylphosphonium bromide (II), an off-white solid (133 g), with a yield of 94.5%.

[0117] (2) Preparation of (R)-5-hydroxymethyldihydrofuran-2-one Formula (III):

[0118] Add trifluoroacetic acid (91.2g, 0.8mol) to a 500ml reaction bottle, then add 30% hydrogen peroxide (79g, 0.7mol) and raise the temperature to 60°C, start to slowly drop 4-pentenoic acid (21g, 0.21mol), add it in 1h, and then keep the temperature for 4h. Concentrate it by rotary evaporation, then add 80ml of methanol and 2.5g of 35% concentrated hydrochloric acid, control the temperature at 30°C, and keep it for 4h. Concentrate it by rotary evaporation to remove the solvent, and obtain (R)-5-hydroxymethyldihydrofuran-2-one formula (III), 22.7g of light yellow liquid, yield 93.2%, gas phase purity 96%.

[0119] (3) Preparation of (R)-5-oxotetrahydrofuran-2-carboxaldehyde Formula (IV):

[0120] Add (R)-5-hydroxymethyldihydrofuran-2-one (22.7g, 0.2mol) to a 2L reaction bottle, add 700ml of anhydrous dichloromethane, start stirring, and control the temperature at 30°C. Then add pyridinium dichromate (150g, 0.4mol) and anhydrous magnesium sulfate (150g) to the system twice, keep stirring at the temperature for 3h. Filter with diatomaceous earth, and directly concentrate the filtered mother liquor by rotary evaporation to dryness to obtain a crude product (R)-5-oxotetrahydrofuran-2-carboxaldehyde (IV).

[0121] (4) Preparation of (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one Formula (I):

[0122] Add nonyltriphenylphosphonium bromide (122g, 0.26mol) to a 1L reaction bottle, add 500ml of anhydrous tetrahydrofuran, start stirring, control the temperature at 5℃, replace and protect the system with nitrogen. Add sodium (trimethylsilyl)amide (66g, 0.36mol) to the system in three times, then raise the temperature to 30℃ and keep it for 1h. Then cool the system to -25℃, slowly drop a mixture of (R)-5-oxotetrahydrofuran-2-carboxaldehyde crude product and 50ml of tetrahydrofuran, and keep it for 30min after the addition is complete. Add water and dichloromethane to extract, dry the organic phase with anhydrous sodium sulfate, concentrate by rotary evaporation, and obtain (R,Z)-5-(1-decene)dihydrofuran-2(3H)-one formula (Ⅰ) after silica gel column chromatography, 37g of colorless liquid, 88% yield of two-step reaction, and 98.3% purity.

[0123] 1 H NMR(300MHz, CDCl3)δ:0.88(t,J=6.9Hz,3H),1.27–1.40(m,12H),1.91–1.98(m,1H),2.06–2.16(m,2H),2.35–2.4 3(m,1H),2.53–2.59(m,2H),5.21–5.29(m,1H),5.42–5.49(m,1H),5.63–5.72(m,1H); (m,1H),5.63–5.72(m,1H).

[0124] The above description is only the preferred embodiment of the present invention, and does not limit the patent scope of the present invention. For those skilled in the art, the present invention may have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention and directly or indirectly applied to other related technical fields shall be included in the protection scope of the present invention.

Claims

1. A process for producing (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one, wherein the (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one has a structure shown in formula (I): The steps include: (1) Using 1-bromononane as a raw material, reacting with triphenylphosphine under certain temperature and solvent conditions, nonyltriphenylphosphonium bromide (II) is obtained; (2) using 4-pentenoic acid as a raw material, an oxidation reaction and an intramolecular esterification reaction are carried out in the presence of an oxidant to obtain the target fragment (R)-5-hydroxymethyldihydrofuran-2-one (III); (3) using (R)-5-hydroxymethyldihydrofuran-2-one (III) as a raw material, adding an oxidant and a desiccant, and obtaining the target fragment (R)-5-oxotetrahydrofuran-2-carboxaldehyde (IV) through an oxidation reaction; (4) Using (R)-5-oxotetrahydrofuran-2-carboxaldehyde (IV) as a raw material and nonyltriphenylphosphonium bromide (II) in the presence of a base, a Wittig reaction is carried out to obtain the target product (R,Z)-5-(1-decene)dihydrofuran-2(3H)-one (I).

2. The production process of (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one according to claim 1, characterized in that: The nonyltriphenylphosphonium bromide described in step (1) has a structure shown in formula (II): Preferably, the reaction in step (1) is carried out in a solvent, and further preferably, the solvent is one or a combination of N,N-dimethylformamide, N,N-dimethylacetamide, toluene, acetonitrile and xylene.

3. The production process of (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one according to claim 1, characterized in that: The temperature in step (1) is controlled at 70°C to 150°C; Preferably, the molar ratio of 1-halononane to triphenylphosphine in the reaction in step (1) is 1:(1-4).

4. The production process of (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one according to claim 1, characterized in that: The (R)-5-hydroxymethyldihydrofuran-2-one described in step (2) has a structure shown in formula (III): Preferably, the oxidant in step (2) is one or a combination of performic acid, peracetic acid, perpropionic acid, perbenzoic acid, meta-chloroperbenzoic acid, trifluoroperacetic acid, formic acid and hydrogen peroxide, acetic acid and hydrogen peroxide, acetic anhydride and hydrogen peroxide, potassium permanganate, and osmium tetroxide.

5. The production process of (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one according to claim 1, characterized in that: In step (2), the molar ratio of the raw material 4-pentenoic acid to the oxidant is 1:(1.1-3); Preferably, the reaction temperature of step (2) is controlled at 20°C to 70°C.

6. The production process of (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one according to claim 1, characterized in that: The (R)-5-oxotetrahydrofuran-2-carboxaldehyde described in step (3) has a structure shown in formula (IV): Preferably, the oxidant in the reaction in step (3) is one or a combination of Dess-Martin oxidant, pyridinium dichromate, chromic acid, pyridinium chlorochromate, pyridinium fluorochromate, and potassium permanganate; Preferably, the desiccant in step (3) is one or a combination of anhydrous magnesium sulfate, silica gel powder, and molecular sieve.

7. The production process of (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one according to claim 1, characterized in that: In step (3), the molar ratio of the raw material (R)-5-hydroxymethyldihydrofuran-2-one to the oxidant is 1:(1-4); Preferably, the reaction temperature of step (3) is controlled at 10°C to 40°C.

8. The production process of (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one according to claim 1, characterized in that: The (R,Z)-5-(1-decene)dihydrofuran-2(3H)-one described in step (4) has the structure shown in formula (I): Preferably, the reaction in step (4) is carried out in a solvent, and further preferably, the solvent is one or a combination of tetrahydrofuran, toluene, N,N-dimethylformamide, and diethyl ether.

9. The production process of (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one according to claim 1, characterized in that: In step (4), the base is one or a combination of potassium bis(trimethylsilyl)amide, lithium bis(trimethylsilyl)amide, sodium bis(trimethylsilyl)amide, trityl sodium, sodium amide, potassium tert-butoxide, lithium diisopropylamide, potassium carbonate, potassium hydroxide, and sodium hydroxide.

10. The production process of (R, Z)-5-(1-decene)dihydrofuran-2(3H)-one according to claim 1, characterized in that: In step (4), the molar ratio of the raw material (R)-5-oxotetrahydrofuran-2-carbaldehyde to the base is 1:(1.1-2.0); Preferably, the reaction temperature of step (4) is controlled at -40°C to 30°C; Preferably, the reaction in step (4) is carried out under a nitrogen atmosphere.

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