CN102942450B - 1-methyl-4-isopropyl-bicyclo[2,2,2]-2,3-dihydroxytoluene-5-octylene, as well as preparation method and application thereof - Google Patents
1-methyl-4-isopropyl-bicyclo[2,2,2]-2,3-dihydroxytoluene-5-octylene, as well as preparation method and application thereof Download PDFInfo
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- CN102942450B CN102942450B CN201210498805.4A CN201210498805A CN102942450B CN 102942450 B CN102942450 B CN 102942450B CN 201210498805 A CN201210498805 A CN 201210498805A CN 102942450 B CN102942450 B CN 102942450B
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Abstract
The invention provides 1-methyl-4-isopropyl-bicyclo[2,2,2]-2,3-dihydroxytoluene-5-octylene with a structural formula as the specification, as well as a preparation method and an application thereof. The preparation process is concise, and has a good reaction effect. The preparation method has the advantages of over 75 percent of reaction conversion rate, no catalyst in the reacting process, mild reaction conditions and low production cost. The 1-methyl-4-isopropyl-bicyclo[2,2,2]-2,3-dihydroxytoluene-5-octylene can be used as an intermediate for synthesizing novel epoxy resin. The novel epoxy resin contains bridge rings, unsaturated double bonds and other structures in the molecular formula.
Description
Technical field
The invention belongs to turps acid anhydrides or terpenes/maleic anhydride adduct reduzate and method for making thereof and application.
Background technology
China's resin resource enriches, and turps annual production reaches 60,000 tons.Terebinthine main application produces the raw material of many important fine chemicals.Turps and maleic anhydride can generate terpenes-maleic anhydride adduct through isomery addition reaction under acid catalysis.Terpinene maleic anhydride is widely used in the aspects such as structural adhesive, epoxy resin-based paint, epoxy composite material and insulating material at present.From the seventies, just there is scholar to conduct extensive research, as US Patent No. 4055576 terpinene maleic anhydride and method for making thereof, purposes; Canadian Patent CA1072565; Chinese patent CN1194980, CN1628929 etc.; But it is less to the research of the further deep processing of terpinene maleic anhydride at present; and China has abundant terpene resource; simultaneously terpenoid has green, the advantage such as harmless, and the novelty teabag therefore developing terpenoid has very important meaning to effectively utilizing China's terpene resource and protection of the environment.
Summary of the invention
The technical problem solved: the invention provides a kind of nontoxic, nonirritant, there is the novel unsaturation bicyclic diterpene derivative of good aqueous solubility, i.e. 1-methyl-4-sec.-propyl-two ring [2,2,2]-2,3-dihydroxymethyl-5-octenes and its preparation method and application.
Technical scheme: 1-methyl-4-sec.-propyl-two ring [2,2,2]-2,3-dihydroxymethyl-5-octene, has following structural formula:
1-methyl-4-sec.-propyl-two ring [2,2,2] preparation method of-2,3-dihydroxymethyl-5-octenes, preparation process is: by α-turps and maleic anhydride, in molar ratio for 1:1 is raw material, at 180 DEG C ~ 200 DEG C, carry out intermolecular Di Ersi-Alder addition reaction, obtain 1-methyl-4-sec.-propyl-dicyclo [2,2,2]-5-octene-2,3-dicarboxylic anhydride; With toluene, dimethyl formamide, tetrahydrofuran (THF) for solvent, at 40 DEG C ~ 70 DEG C, lithium aluminum hydride and 1-methyl-4-sec.-propyl-dicyclo [2,2,2]-5-octene-2,3-dicarboxylic anhydride take mass ratio as 1:10 ~ 1:20 reaction 8 ~ 48 hours, then add water (be 10:1 ~ 50:1 with the mass ratio of lithium aluminum hydride), massfraction is 15% ~ 40%NaOH (be 20:1 ~ 50:1 with the mass ratio of lithium aluminum hydride) solution, filter, underpressure distillation, obtains product, called after 1-methyl-4-sec.-propyl-two ring [2,2,2]-2,3-dihydroxymethyl-5-octenes.
1-methyl-4-sec.-propyl-two ring [2,2,2]-2,3-dihydroxymethyl-5-octene is preparing the application in terpenes epoxy resin.
Reaction formula is as follows:
Beneficial effect:
1. preparation technology of the present invention is succinct, reaction effect good.Its advantage is that the transformation efficiency of reaction is high, reaches more than 75%, does not need to add catalyzer in reaction process, and reaction conditions is gentle, and production cost is low.
2. 1-methyl-4-sec.-propyl-two ring [2,2,2]-2, the 3-dihydroxymethyl-5-octene that prepared by the present invention can as the intermediate of a kind of neo-epoxy resin of synthesis.Containing bridged ring in this novel epoxy molecule formula, the structures such as unsaturated double-bond.
Accompanying drawing explanation
Fig. 1 is the infrared spectrum of 1-methyl-4-sec.-propyl-dicyclo [2,2,2]-5-octene-2,3-dicarboxylic anhydride (being called for short terpinene maleic anhydride or HTMA);
Fig. 2 is 1-methyl-4-sec.-propyl-dicyclo [2,2,2]-5-octene-2,3-dicarboxylic anhydride (being called for short terpinene maleic anhydride or HTMA)
1h-NMR schemes;
Fig. 3 is the infrared spectrum that 1-methyl-4-sec.-propyl-two ring [2,2,2]-2,3-dihydroxymethyl-5-octene is called for short (MIBOD);
Fig. 4 is that 1-methyl-4-sec.-propyl-two ring [2,2,2]-2,3-dihydroxymethyl-5-octene is called for short (MIBOD)
1h-NMR;
Fig. 5 is a kind of infrared spectrum of novel terpenes epoxy resin.
Embodiment
Further illustrate the present invention by specific embodiment below, but the present invention is not limited.Raw material of the present invention, equipment and reagent unless otherwise indicated all commercially, or can obtain according to the preparation of this area ordinary method.Unless otherwise defined or illustrate, all specialties used herein and scientific words and those skilled in the art the same meaning be familiar with.
Embodiment 1
Get 98g maleic anhydride to add in the four-hole boiling flask that thermometer, whipping appts, dropping funnel, prolong are housed, be heated to melting, stir, at 180 DEG C, drip the α-turps 170g containing 0.15g iodine.After dropwising, be warmed up to 200 DEG C, at 200 DEG C of reaction 2h.Underpressure distillation obtains 1-methyl-4-sec.-propyl-dicyclo [2,2,2]-5-octene-2,3-dicarboxylic anhydride, with FT-IR,
1h-NMR characterizes reaction product, its FT-IR,
1h-NMR schemes as accompanying drawing 1, shown in accompanying drawing 2.Spectrum Analysis: IR (v, cm
-1): 2960,2873,1835,1770,1461,1372,1216,1080,1004;
1h-NMR (б, ppm): 6.0,3.2,2.8,2.5,1.5,1.0,0.7.
Embodiment 2
Underpressure distillation product 1-methyl-4-sec.-propyl-dicyclo [2 that Example 1 obtains, 2,2]-5-octene-2,3-dicarboxylic anhydride 10g is dissolved in 40mL tetrahydrofuran (THF), then joins mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube are housed (prolong meet built-in CaCl
2drying tube) 250mL four-hole boiling flask in, from constant pressure funnel drip be dissolved with lithium aluminum hydride (m
liAlH4=1g) tetrahydrofuran solution 40mL, dropwise rear back flow reaction 8h.After reaction terminates, add 40mL distilled water, the sodium hydroxide solution 40mL of 15%wt, filter, washing, underpressure distillation steams solvent, obtains reaction product 1-methyl-4-sec.-propyl-two ring [2,2,2]-2,3-dihydroxymethyl-5-octene, the transformation efficiency of product reaches 75%, uses FT-IR
1h-NMR characterizes reaction product, its FT-IR,
1h-NMR schemes as accompanying drawing 3, shown in accompanying drawing 4.Spectrum Analysis: IR (v, cm
-1): 3280,2953,2870,1570,1400,1120,1027;
1h-NMR (б, ppm): 6.0,4.2,3.7,3.4,2.8,2.5,1.8,1.4,1.0,0.8,0.5.
Embodiment 3
Underpressure distillation product 1-methyl-4-sec.-propyl-dicyclo [2 that Example 1 obtains, 2,2]-5-octene-2,3-dicarboxylic anhydride 10g is dissolved in 40mL toluene, then joins mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube are housed (prolong meet built-in CaCl
2drying tube) 250mL four-hole boiling flask in, from constant pressure funnel drip be dissolved with lithium aluminum hydride (m
liAlH4=1g) tetrahydrofuran solution 40mL, dropwise rear back flow reaction 8h.After reaction terminates, add 40mL distilled water, the sodium hydroxide solution 40mL of 15%wt, filter, washing, underpressure distillation steams solvent, obtains reaction product 1-methyl-4-sec.-propyl-two ring [2,2,2]-2,3-dihydroxymethyl-5-octenes, the transformation efficiency of product reaches 50%.With FT-IR,
1h-NMR characterizes reaction product, its FT-IR,
1h-NMR schemes as accompanying drawing 3, shown in accompanying drawing 4.Spectrum Analysis: IR (v, cm
-1): 3280,2953,2870,1570,1400,1120,1027;
1h-NMR (б, ppm): 6.0,4.2,3.7,3.4,2.8,2.5,1.8,1.4,1.0,0.8,05.
Embodiment 4
Underpressure distillation product 1-methyl-4-sec.-propyl-dicyclo [2 that Example 1 obtains, 2,2]-5-octene-2,3-dicarboxylic anhydride 10g is dissolved in 40mL dimethyl formamide, then joins mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube are housed (prolong meet built-in CaCl
2drying tube) 250mL four-hole boiling flask in, from constant pressure funnel drip be dissolved with lithium aluminum hydride (m
liAlH4=1g) tetrahydrofuran solution 40mL, dropwise rear back flow reaction 8h.After reaction terminates, add 40mL distilled water, the sodium hydroxide solution 40mL of 15%wt, filter, washing, underpressure distillation steams solvent, obtains reaction product 1-methyl-4-sec.-propyl-two ring [2,2,2]-2,3-dihydroxymethyl-5-octenes, the transformation efficiency of product reaches 40%.With FT-IR,
1h-NMR characterizes reaction product, its FT-IR,
1h-NMR schemes as accompanying drawing 3, shown in accompanying drawing 4.Spectrum Analysis: IR (v, cm
-1): 3280,2953,2870,1570,1400,1120,1027;
1h-NMR (б, ppm): 6.0,4.2,3.7,3.4,2.8,2.5,1.8,1.4,1.0,0.8,0.5.
Embodiment 5
Underpressure distillation product 1-methyl-4-sec.-propyl-dicyclo [2 that Example 1 obtains, 2,2]-5-octene-2,3-dicarboxylic anhydride 20g is dissolved in 40mL tetrahydrofuran (THF), then joins mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube are housed (prolong meet built-in CaCl
2drying tube) 250mL four-hole boiling flask in, from constant pressure funnel drip be dissolved with lithium aluminum hydride (m
liAlH4=1g) tetrahydrofuran solution 40mL, dropwise rear back flow reaction 8h.After reaction terminates, add 40mL distilled water, the sodium hydroxide solution 40mL of 15%wt, filter, washing, underpressure distillation steams solvent, obtains reaction product 1-methyl-4-sec.-propyl-two ring [2,2,2]-2,3-dihydroxymethyl-5-octenes, the transformation efficiency of product reaches 50%.With FT-IR,
1h-NMR characterizes reaction product, its FT-IR,
1h-NMR schemes as accompanying drawing 3, shown in accompanying drawing 4.Spectrum Analysis: IR (v, cm
-1): 3280,2953,2870,1570,1400,1120,1027;
1h-NMR (б, ppm): 6.0,4.2,3.7,3.4,2.8,2.5,1.8,1.4,1.0,0.8,0.5.
Embodiment 6
Underpressure distillation product 1-methyl-4-sec.-propyl-dicyclo [2 that Example 1 obtains, 2,2]-5-octene-2,3-dicarboxylic anhydride 10g is dissolved in 40mL tetrahydrofuran (THF), then joins mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube are housed (prolong meet built-in CaCl
2drying tube) 250mL four-hole boiling flask in, from constant pressure funnel drip be dissolved with lithium aluminum hydride (m
liAlH4=1g) tetrahydrofuran solution 40mL, dropwise rear back flow reaction 24h.After reaction terminates, add 40mL distilled water, the sodium hydroxide solution 40mL of 15%wt, filter, washing, underpressure distillation steams solvent, obtains reaction product 1-methyl-4-sec.-propyl-two ring [2,2,2]-2,3-dihydroxymethyl-5-octenes, the transformation efficiency of product reaches 80%.With FT-IR,
1h-NMR characterizes reaction product, its FT-IR,
1h-NMR schemes as accompanying drawing 3, shown in accompanying drawing 4.Spectrum Analysis: IR (v, cm
-1): 3280,2953,2870,1570,1400,1120,1027;
1h-NMR (б, ppm): 6.0,4.2,3.7,3.4,2.8,2.5,1.8,1.4,1.0,0.8,0.5.
Embodiment 7
Underpressure distillation product 1-methyl-4-sec.-propyl-dicyclo [2 that Example 1 obtains, 2,2]-5-octene-2,3-dicarboxylic anhydride 10g is dissolved in 40mL tetrahydrofuran (THF), then joins mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube are housed (prolong meet built-in CaCl
2drying tube) 250mL four-hole boiling flask in, from constant pressure funnel drip be dissolved with lithium aluminum hydride (m
liAlH4=1g) tetrahydrofuran solution 40mL, dropwise rear back flow reaction 48h.After reaction terminates, add 40mL distilled water, the sodium hydroxide solution 40mL of 15%wt, filter, washing, underpressure distillation steams solvent, obtains reaction product 1-methyl-4-sec.-propyl-two ring [2,2,2]-2,3-dihydroxymethyl-5-octenes, the transformation efficiency of product reaches 85%.With FT-IR,
1h-NMR characterizes reaction product, its FT-IR,
1h-NMR schemes as accompanying drawing 3, shown in accompanying drawing 4.Spectrum Analysis: IR (v, cm
-1): 3280,2953,2870,1570,1400,1120,1027;
1h-NMR (б, ppm): 6.0,4.2,3.7,3.4,2.8,2.5,1.8,1.4,1.0,0.8,0.5.
Embodiment 8
Underpressure distillation product 1-methyl-4-sec.-propyl-two ring [2 that Example 7 obtains, 2,2]-2,3-dihydroxymethyl-5-octene 1g adds in the four-hole boiling flask that thermometer, whipping appts, dropping funnel, prolong are housed, then the epoxy chloropropane of 6g is added, 0.01g benzyltriethylammoinium chloride, 0.36g sodium hydroxide, reacts 2h at 80 DEG C.Reaction terminates rear filtration, and underpressure distillation obtains a kind of novel terpenes epoxy resin.Its oxirane value reaches 3.5mmol/g, viscosity 1.7Pas (50 DEG C).With FT-IR, terpenes epoxy resin is characterized, its FT-IR, as shown in Figure 5.Spectrum Analysis: IR (v, cm
-1): 3412,2957,2872,1735,1458,1372,1245,1171,1054,1032,1010.
Claims (1)
1.1-methyl-4-sec.-propyl-two ring [2,2,2]-2,3-dihydroxymethyl-5-octene is preparing the application in terpenes epoxy resin, it is characterized in that getting 98 g maleic anhydrides adds in the four-hole boiling flask that thermometer, whipping appts, dropping funnel, prolong are housed, be heated to melting, stir, at 180 DEG C, drip α-turps 170 g containing 0.15 g iodine; After dropwising, be warmed up to 200 DEG C, at 200 DEG C of reaction 2 h; Underpressure distillation obtains 1-methyl-4-sec.-propyl-dicyclo [2,2,2]-5-octene-2,3-dicarboxylic anhydride; The underpressure distillation product 1-methyl-4-sec.-propyl-dicyclo [2 obtained, 2,2]-5-octene-2,3-dicarboxylic anhydride 10 g is dissolved in 40 mL tetrahydrofuran (THF)s, then join in the four-hole boiling flask of 250 mL that mechanical stirring device, thermometer, constant pressure funnel and reflux condensing tube are housed, prolong meets built-in CaCl
2drying tube, drip from constant pressure funnel and be dissolved with tetrahydrofuran solution 40 mL of lithium aluminum hydride, m
liAlH4=1 g, dropwises rear back flow reaction 48 h; After reaction terminates, add 40 mL distilled water, sodium hydroxide solution 40 mL of 15 %wt, filter, washing, underpressure distillation steams solvent, obtains reaction product 1-methyl-4-sec.-propyl-two ring [2,2,2]-2,3-dihydroxymethyl-5-octene; Underpressure distillation product 1-methyl-4-sec.-propyl-two ring [2 obtained, 2,2]-2,3-dihydroxymethyl-5-octene 1 g adds in the four-hole boiling flask that thermometer, whipping appts, dropping funnel, prolong are housed, and then adds the epoxy chloropropane of 6 g, 0.01 g benzyltriethylammoinium chloride, 0.36 g sodium hydroxide, at 80 DEG C, react 2 h, reaction terminates rear filtration, and underpressure distillation obtains a kind of terpenes epoxy resin.
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| CN100491435C (en) * | 2007-04-29 | 2009-05-27 | 中国林业科学研究院林产化学工业研究所 | Method of preparing hydrogenated terpinene maleic anhydride glycidyl ester type epoxy resin |
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