CN104262319A - Nopylaldehyde hydride cyclic acetal compound and synthesis method thereof - Google Patents
Nopylaldehyde hydride cyclic acetal compound and synthesis method thereof Download PDFInfo
- Publication number
- CN104262319A CN104262319A CN201410404759.6A CN201410404759A CN104262319A CN 104262319 A CN104262319 A CN 104262319A CN 201410404759 A CN201410404759 A CN 201410404759A CN 104262319 A CN104262319 A CN 104262319A
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- Prior art keywords
- aldehyde
- hydride
- cyclic acetal
- nopylaldehyde
- hydrogenation
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- 0 C*1C2C(CC3(C)OCCCO3)C=CCC1C2 Chemical compound C*1C2C(CC3(C)OCCCO3)C=CCC1C2 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/10—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings
- C07D317/12—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 not condensed with other rings with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to ring carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a nopylaldehyde hydride cyclic acetal compound and a synthesis method thereof. The ring formation part of the structural formula of the compound comprises a parallel cycle and a monocycle, wherein the parallel cycle is nopyl hydride serving as a parent; and the monocycle is cyclic acetal generated by nopylaldehyde hydride and three kinds of dihydric alcohols; and three kinds of nopylaldehyde hydride cyclic acetal compounds are obtained by catalyzing the nopylaldehyde hydride, ethylene glycol, 1,2-propylene glycol and 1,3-propylene glycol through oxalic acid and dehydrating the mixture through a water carrying agent. Three kinds of novel compounds are synthesized by using an efficient, rapid and environmentally-friendly method, the yield is 62-87 percent, and the compounds have good inhibiting effects on Colletotrichum loquat, Colletotrichum camelliae, phytophthora capsici, Rhizoctonia solani, magnapothe grisea and lettuce sclerotium.
Description
Technical field
The present invention relates to the field of chemical synthesis, specifically aldehyde cyclic acetal compounds and synthetic method thereof are foretold in a kind of hydrogenation promise.
Background technology
China is a large agricultural country, and the relations of production of farm crop national economy.Current, rice blast, rice sheath blight disease, anthrax are global corps diseases, have a strong impact on agriculture production and grain security.The large multiplex sterilant of the method for this quasi-microorganism of current minimizing to the harm of farm crop controls.As everyone knows, sterilant comprises organic phosphates, benzene class and heterocyclic compound, and these compounds all have negative impact to human body and environment, therefore in the urgent need to finding a kind of sterilant of green non-pollution.Plant-sourced terpenoid has aromaticity, user be easy to accept, the more important thing is they derive from natural, toxicity is low, pungency is little, to the mankind and environmental friendliness.
Acetal compound has pleasant fragrance usually, and stable in properties, be used for daily chemical industry.In addition, acetal compound has some biological activitys.In recent years, research shows that some hydrogenation nopol derivatives have repellent action to monomorium pharaonis, Aedes albopictus and small cabbage moth, also not yet launches the research of anti-microbial activity.
Summary of the invention
The object of the present invention is to provide a kind of productive rate high and the hydrogenation promise that anti-microbial property is good fore-telling aldehyde cyclic acetal compounds and synthetic method thereof, to solve the problem proposed in above-mentioned background technology.
For achieving the above object, the invention provides following technical scheme:
Aldehyde cyclic acetal compounds is foretold in a kind of hydrogenation promise, and structural formula is as follows:
Wherein, this compound by monocycle and and ring form, monocycle is that hydrogenation promise is foretold aldehyde and dibasic alcohol and generated through condensation reaction, and ring is parent hydrogenation promise fore-telling.
The synthetic method of aldehyde cyclic acetal compounds is foretold in a kind of hydrogenation promise, concrete steps are as follows: the ratio that hydrogenation promise fore-telling aldehyde and dibasic alcohol are 1: 2 by (1) in molar ratio puts into Erlenmeyer flask, add oxalic acid as catalyzer, load onto water trap (adding azeotropic agent) and prolong, carry out heated and stirred, to treat in water trap no longer muddiness and stopped reaction; (2) extracted by reacted product benzene, extraction liquid saturated aqueous common salt washes twice, then carries out underpressure distillation after anhydrous sodium sulfate drying, collects cut; (3) the cut gc analysis purity of will collect, carries out structural analysis.
General structure after product analysis is as follows:
Compared with prior art, the invention has the beneficial effects as follows: utilize method that is efficient, quick, environmental protection to synthesize three kinds of new compounds, productive rate, between 62% ~ 87%, has good restraining effect to rake anthrax bacteria, Oil Tea Anthracnose bacterium, phytophthora capsici, Rhizoctonia solani Kuhn, rice blast fungus and lettuce sclerotium.
Embodiment
Below in conjunction with the embodiment of the present invention, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
Aldehyde cyclic acetal compounds is foretold in hydrogenation promise, and structural formula is as follows:
Wherein, this compound by monocycle and and ring form, monocycle is that hydrogenation promise is foretold aldehyde and dibasic alcohol and generated through condensation reaction, and ring is parent hydrogenation promise fore-telling.
Embodiment 1
The synthetic method of aldehyde Glycol Acetal is foretold in a kind of hydrogenation promise, concrete steps are as follows: (1) aldehyde is foretold in 0.1mol hydrogenation promise and Erlenmeyer flask put into by 0.2mol ethylene glycol, add 0.5g oxalic acid as catalyzer, load onto water trap (adding azeotropic agent) and prolong, carry out heated and stirred, to treat in water trap no longer muddiness and stopped reaction; (2) extracted by reacted product benzene, extraction liquid saturated aqueous common salt washes twice, then carries out underpressure distillation after anhydrous sodium sulfate drying, collects cut, obtains 4.9g hydrogenation promise and foretells aldehyde Glycol Acetal (2a); (3) the cut gc analysis purity of will collect, carries out structural analysis.
The chemosynthesis formula of aldehyde Glycol Acetal is foretold in hydrogenation promise:
The yield that aldehyde Glycol Acetal is foretold in hydrogenation promise is 87.9%, GC purity assay 93.1%, and this compound is colourless liquid, b.p.135 ~ 136 DEG C/18mmHg,
1.4822.
FT-IR(cm
-1)：2982，2940，2878(C-H)，1469，1408(CH
2)，1383，1366(CMe
2)，1136，1048.9(C-O-C)；
EI-MSm/z(RA％)：155(100)，210(M
+，8.76)；
1HNMR，δ
H(ppm)：4.83(1H，11-CH)，3.95，3.81(2H，2H，2S，OCH
2CH
2O)，2.29～2.23(2H，m，
10-CH
2)，2.03～1.71(7H，m，1-CH，
2-CH，
3-CH，
4-CH
2，
5-CH)，1.55～1.48(1H，m，
7-CH)，1.17(3H，S，
9-CH
3)，1.00(3H，S，
8-CH
3)，0.89(1H，d，J＝8Hz，
7-CH)；
13CNMR，δ
C(ppm)：103.898(
11-C)，64.658(
α-C)，64.566(
α′-C)，46.502(
2-C)，41.769(
10-C)，41.193(
1-C)，38.566(
6-C)，36.793(
5-C)，33.362(
7-C)，28.036(
9-CH
3)，26.353(
4-C)，23.138(
8-C)，22.351(
3-C)。
Embodiment 2
Aldehyde 1 is foretold in a kind of hydrogenation promise, the synthetic method of 2-propylene glycol acetal, concrete steps are as follows: 0.1mol hydrogenation promise is foretold 1 of aldehyde and 0.2mol by (1), Erlenmeyer flask put into by 2-propylene glycol, add 0.5g oxalic acid as catalyzer, load onto water trap (adding azeotropic agent) and prolong, carry out heated and stirred, to treat in water trap no longer muddiness and stopped reaction; (2) extracted by reacted product benzene, extraction liquid saturated aqueous common salt washes twice, then carries out underpressure distillation after anhydrous sodium sulfate drying, collects cut, obtains 10.6g hydrogenation promise and foretells aldehyde 1,2-PD acetal (2b); (3) the cut gc analysis purity of will collect, carries out structural analysis.
The chemosynthesis formula of aldehyde 1,2-PD acetal is foretold in hydrogenation promise:
The yield that aldehyde 1,2-PD acetal is foretold in hydrogenation promise is 66.3%, GC purity assay 96.1%, and this compound is colourless liquid, b.p.136 ~ 137 DEG C/17mmHg,
1.4898.
FT-IR(cm
-1)：2985，2937，2904，2872(C-H)，1468，1413(CH
2)，1382(CMe
2)，1141，1047(C-O-C)；
EI-MSm/z(RA％)：167(100)，224(M
+，7.84)；
1HNMR，δ
H(ppm)：4.89(1H，
11-CH)，4.13(1H，m，CH)，3.90(1H，m，CH)，3.39(1H，m，CH)，2.29～2.22(2H，m，
10-CH
2)，2.03～1.70(7H，m，
1-CH，
2-CH，
3-CH，
4-CH
2，
5-CH)，1.53-1.47(1H，m，
7-CH)，1.27(3H，d，J＝8Hz，
β-CH
3)，1.16(3H，s，
9-CH
3)，0.98(3H，s，
8-CH
3)，0.90(1H，d，J＝8Hz，
7-CH)；
13CNMR，δ
C(ppm)：103.837(
11-C)，72.568(
α-C)，70.615(
α′-C)，46.514(
2-C)，42.259(
10-C)，41.177(
1-C)，38.568(
6-C)，36.682(
5-C)，33.334(
7-C)，28.035(
9-C)，26.357(
4-C)，23.138(
8-C)，22.359(
3-C)，18.687(
3-C)。
Embodiment 3
Aldehyde 1 is foretold in a kind of hydrogenation promise, the synthetic method of ammediol acetal, concrete steps are as follows: 0.1mol hydrogenation promise is foretold 1 of aldehyde and 0.2mol by (1), ammediol puts into Erlenmeyer flask, add 0.5g oxalic acid as catalyzer, load onto water trap (adding azeotropic agent) and prolong, carry out heated and stirred, to treat in water trap no longer muddiness and stopped reaction; (2) extracted by reacted product benzene, extraction liquid saturated aqueous common salt washes twice, then carries out underpressure distillation after anhydrous sodium sulfate drying, collects cut, obtains 13.9g hydrogenation promise and foretells aldehyde 1,3-PD acetal (2c); (3) the cut gc analysis purity of will collect, carries out structural analysis.
The chemosynthesis formula of aldehyde 1,3-PD acetal is foretold in hydrogenation promise:
The yield that aldehyde 1,3-PD acetal is foretold in hydrogenation promise is 62.1%, GC purity assay is 97.5%, is colourless liquid when this compound steams, b.p.134 ~ 136 DEG C/15mmHg,
1.5006.
FT-IR，v
max(cm
-1)：2937，2919(C-H)，1468，1431，1402(CH
2)，1377(CMe
2)，1144(C-O-C)；
EI-MSm/z(RA％)：148(100)，224(M
+，10.72)；
1HNMR，δ
H(ppm)：4.53(1H，
11-CH)，4.09，3.75(2H，2H，t，t，
α-CH
2，
α′-CH
2)，2.31～2.20(2H，m，
10-CH
2)，2.10～1.85(6H，m，
1-CH，
2-CH，
3-CH，
4-CH
2，
5-CH)，1.71(2H，m，
β-CH
2)，1.50(1H，m，
7-CH)，1.34(1H，m，
3-CH)，1.18(3H，s，
9-CH
3)，1.01(3H，s，
8-CH
3)，0.90(1H，d，J＝8Hz，7-CH)；
13CNMR，δ
C(ppm)：101.340(
11-C)，66.774(
α-C/
α′-C)，46.357(
2-C)，43.070(
2-C)，41.173(
1-C)，38.502(
6-C)，35.911(
5-C)，33.402(
7-C)，28.036(
9-C)，26.292(
4-C)，25.765(
β-C)，23.071(
8-C)，22.248(
3-C)。
Aldehyde Glycol Acetal is foretold in hydrogenation promise, aldehyde 1 is foretold in hydrogenation promise, aldehyde 1 is foretold in 2-propylene glycol acetal and hydrogenation promise, ammediol acetal bacteriostatic action, measures the bacteriostasis rate of above-mentioned three kinds of compounds to loquat anthrax bacteria, Oil Tea Anthracnose bacterium, phytophthora capsici, Rhizoctonia solani Kuhn, rice blast fungus and lettuce sclerotium 6 kinds of fungies according to growth rate method.
(1) bacteriostatic activity test
A () aseptically configure ten thousand/ tween-80 (polyoxyethylenesorbitan sorbitan monooleate) pure water solution, above-claimed cpd is configured to the solution for standby that concentration is 1000mg/L; B () is got 6mL solution respectively and is poured in the 45mL substratum of 45 DEG C, pour into respectively in the culture dish of three high 9cm after fully shaking up again, and obtains the flat board that concentration is 100mg/L; C () accesses the bacterium block that diameter is 5mm in flat board after drying, often group does three contrasts, ten thousand/ tween 80 solution do control group, be placed in 28 DEG C of constant incubators and cultivate 3 ~ 4 days, adopt right-angled intersection method to measure bacterium loop diameter; (4) calculate bacteriostasis rate, bacteriostasis rate calculation formula is:
Inhibiting rate (%)=[(control group colony diameter-treatment group colony diameter)/control group colony diameter] × 100.
(2) result
Detected by aforesaid method: compound 2a, 2b, 2c all have restraining effect in various degree to loquat anthrax bacteria, Oil Tea Anthracnose bacterium, phytophthora capsici, Rhizoctonia solani Kuhn, rice blast fungus and lettuce sclerotium under 100mg/L.
Wherein compound 2c is to phytophthora capsici bacteriostasis rate up to 100%, and compound 2b reaches 98.78% to Rhizoctonia solani Kuhn bacteriostasis rate, all has very high bacteriostatic activity; Compound 2a and 2c to Oil Tea Anthracnose bacterium, 2b to lettuce sclerotium, 2c to the bacteriostasis rate of Rhizoctonia solani Kuhn all more than 80%, there is stronger bacteriostatic activity.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and when not deviating from spirit of the present invention or essential characteristic, the present invention can be realized in other specific forms.Therefore, no matter from which point, all should embodiment be regarded as exemplary, and be nonrestrictive, scope of the present invention is limited by claims instead of above-mentioned explanation, and all changes be therefore intended in the implication of the equivalency by dropping on claim and scope are included in the present invention.
Claims (2)
1. an aldehyde cyclic acetal compounds is foretold in hydrogenation promise, and it is characterized in that, structural formula is as follows:
Wherein, this compound by monocycle and and ring form, monocycle is that hydrogenation promise is foretold aldehyde and dibasic alcohol and generated through condensation reaction, and ring is parent hydrogenation nopyl.
2. the synthetic method of a hydrogenation promise fore-telling aldehyde cyclic acetal compounds as claimed in claim 1, it is characterized in that, concrete steps are as follows: the ratio that hydrogenation promise fore-telling aldehyde and dibasic alcohol are 1: 2 by (1) in molar ratio puts into Erlenmeyer flask, add oxalic acid as catalyzer, load onto water trap (adding azeotropic agent) and prolong, carry out heated and stirred, to treat in water trap no longer muddiness and stopped reaction; (2) extracted by reacted product benzene, extraction liquid saturated aqueous common salt washes twice, then carries out underpressure distillation after anhydrous sodium sulfate drying, collects cut; (3) the cut gc analysis purity of will collect, carries out structural analysis.
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| CN201410404759.6A CN104262319B (en) | 2014-08-14 | 2014-08-14 | Aldehyde cyclic acetal compounds and synthetic method thereof are foretold in a kind of hydrogenation promise |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632229A (en) * | 2015-11-04 | 2017-05-10 | 中国科学院大连化学物理研究所 | Preparation method of cyclic acetal |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0018504A1 (en) * | 1979-04-07 | 1980-11-12 | Henkel Kommanditgesellschaft auf Aktien | Use of aldehydes as microbicides |
| US5510326A (en) * | 1994-12-23 | 1996-04-23 | Givaudan-Roure Corporation | Multi-substituted tetrahydrofurans |
-
2014
- 2014-08-14 CN CN201410404759.6A patent/CN104262319B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0018504A1 (en) * | 1979-04-07 | 1980-11-12 | Henkel Kommanditgesellschaft auf Aktien | Use of aldehydes as microbicides |
| US5510326A (en) * | 1994-12-23 | 1996-04-23 | Givaudan-Roure Corporation | Multi-substituted tetrahydrofurans |
Non-Patent Citations (2)
| Title |
|---|
| MARINA C. DE FREITAS等: "Synthesis of Fragrance Compounds from Biorenewables: Tandem Hydroformylation–Acetalization of Bicyclic Monoterpenes", 《CHEMCATCHEM》, vol. 5, 3 May 2013 (2013-05-03), pages 1884 - 1890, XP055110229, DOI: doi:10.1002/cctc.201200948 * |
| 王宗德 等: "诺卜醇及其衍生物的合成与应用", 《林产化工通讯》, vol. 35, no. 6, 31 December 2001 (2001-12-31), pages 25 - 29 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106632229A (en) * | 2015-11-04 | 2017-05-10 | 中国科学院大连化学物理研究所 | Preparation method of cyclic acetal |
| CN106632229B (en) * | 2015-11-04 | 2019-04-05 | 中国科学院大连化学物理研究所 | A kind of preparation method of cyclic acetal |
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| Publication number | Publication date |
|---|---|
| CN104262319B (en) | 2016-08-24 |
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