CN103121989B - Synthesis method of spiroxamine as bactericide - Google Patents
Synthesis method of spiroxamine as bactericide Download PDFInfo
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Abstract
The invention discloses a synthesis method of spiroxamine as a bactericide. The synthesis method comprises the following steps of: (1) subjecting a compound X and alkylamine to a reaction under the action of alkali to obtain a compound XI; and (2) subjecting the compound XI, alkyl bromide and alkali to a reaction under the action of a phase transfer catalyst to obtain a compound I, wherein R1 is C1-4 alkyl group or C1-4 alkyl phenyl, and R2 is n-propyl or ethyl. The synthesis method is low in cost, simple and convenient for reaction operation, mild in experiment condition, little in pollution, high in reaction yield in each step and suitable for industrial production.
Description
Technical field
The invention belongs to sterilant synthesis field, be specifically related to a kind of new synthetic method of sterilant volution bacterium amine.
Background technology
Volution bacterium amine, spiral shell dislikes luxuriant amine to another name, spiral shell dislikes luxuriant amine, the N-ethyl-N-propyl group-8-tertiary butyl-1,4-dioxo spiro [4.5] decane-2-methylamine, its English name Spiroxamine, English another name N-Ethyl-N-propyl-8-tert-butyl-1,4-dioxaspiro [4.5] dec-2-ylmethylamine, its CAS NO.118134-30-8, molecular formula C
18h
35nO
2, molecular weight 297.48.
The volution bacterium amine mechanism of action and feature: sterol biosynthesis inhibitor, the main synthesis suppressing C-14 demethylation enzyme.Application: suitable for crop and security Wheat and barley.Under recommended dose to crop safety, without poisoning.Controlling object wheat powdery mildew and various rust, barley leaf blotch and stripe disease.Volution bacterium amine is a kind of foliage fungicide of novel, interior absorption, effective especially to Powdery Mildew.Speed of action is fast and the lasting period is long, has protection and therapeutic action concurrently.Both can be used alone, again can with other fungicide compoundings to expand fungicidal spectrum.Volution bacterium amine is in the wide market of China, and thus its study on the synthesis is significant.
For the preparation of volution bacterium amine, bibliographical information related compound method is as follows:
Synthetic method one by MANETIC RESONANCE IN CHEMISTRY, VOL.36,64
68 (1998), the synthetic method that report compound has chirality VI is as follows:
Reaction reagent and condition: (a) Tosyl chloride, triethylamine, ethylene dichloride, yield 88.2%; (b) 1N hydrochloric acid, acetone, 95.4%; (c) 4-tbutylcyclohexanone, tosic acid, toluene, yield 86.4%; (d) N-ethyl Tri N-Propyl Amine.
This synthetic method has the following disadvantages: raw materials cost is higher, is not suitable for extensive preparation.
Synthetic method two DE19529090A1 reports that the synthetic method of Compound I is as follows:
This synthetic method has the following disadvantages: N-ethyl Tri N-Propyl Amine raw materials cost is higher, is not suitable for extensive preparation.
Summary of the invention
The object of the invention is to solve the raw materials cost such as N-ethyl Tri N-Propyl Amine in existing volution bacterium amine preparation technology expensive, intermediate is not easily purified, cannot the technical problem such as scale operation, provides a kind of synthetic method of high-efficiency low-toxicity sterilant volution bacterium amine.
Object of the present invention can be reached by following measures:
A synthetic method for sterilant volution bacterium amine, it comprises the steps:
(1) compounds X under alkali effect with alkylamine, obtain compounds X I;
(2) Compound I is obtained by reacting under compounds X I and alkyl bromide and alkali effect;
Its reaction equation is as follows:
Wherein, R1 is C
1 ~ 4alkyl or C
1 ~ 4alkyl phenyl, is preferably methyl or 4-aminomethyl phenyl; R2 is n-propyl or ethyl.
In step (1), described alkali can adopt carbonate, as salt of wormwood, sodium carbonate etc., preferably adopts salt of wormwood.Described alkylamine is ethamine, Tri N-Propyl Amine, ethylamine solution or the Tri N-Propyl Amine aqueous solution, and wherein the mass concentration of ethylamine solution or the Tri N-Propyl Amine aqueous solution is 50 ~ 80%, preferably 50 ~ 60%.
In step (1), the mol ratio of compounds X and alkylamine and alkali is 1.0:1.5 ~ 10:1.0 ~ 3.0, preferred 10:20 ~ 30:105 ~ 12.
In step (1), its temperature of reaction is 80 ~ 150 DEG C, preferably 80 ~ 120 DEG C, and reaction solvent is that ethanol is or/and water; Reaction is carried out further in sealing system, and reaction pressure is 0.1 ~ 1.0MPa, preferably 0.3 ~ 0.8MPa.
In step (2), described alkyl bromide is positive propyl bromo or monobromoethane, and step (2) is not identical with the alkyl bromide in (1); Described alkali can adopt carbonate, as salt of wormwood, sodium carbonate etc., preferably adopts salt of wormwood.The reaction of step (2) is carried out further under phase-transfer catalyst, described phase-transfer catalyst is benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride or tetradecyl trimethyl ammonium chloride, preferred tributyl brometo de amonio.
In step (2), the mol ratio of compounds X I and alkali and alkyl bromide is 1.0:1.0 ~ 1.5:1.2 ~ 3.0, preferred 1.0:1.05 ~ 1.2:1.2 ~ 1.5.
In step (2), its temperature of reaction is 40 ~ 200 DEG C, preferably 80 ~ 130 DEG C; Reaction is carried out further in sealing system, and reaction pressure is 0.1 ~ 1.0MPa, preferably 0.3 ~ 0.8MPa.
In step (2), reaction solvent can be the nonhomogeneous system of water and organic solvent composition, can be also single organic solvent system, as ethanol, and preferably water and ethylene dichloride mixed solvent or ethanol in this reactions steps.
Monobromoethane in the present invention refers to monobromethane, i.e. 1-monobromethane.Positive propyl bromo in the present invention refers to N-PROPYLE BROMIDE, i.e. 1-N-PROPYLE BROMIDE.
Reaction in the present invention is carried out referring to that reaction process is not carrying out with the external world carrying out in the reaction compartment of exchange of substance, such as, react and carry out in closed reactor, sealed can or autoclave in sealing system.
Present method solves the raw materials cost such as N-ethyl Tri N-Propyl Amine in existing volution bacterium amine preparation technology expensive, intermediate is not easily purified, cannot the technical problem such as scale operation.Cost of the present invention is low, and operation is easy, and experiment condition is gentle, pollutes little, and each step reaction yield is high, is applicable to suitability for industrialized production.
Embodiment
Below in conjunction with embodiment, the present invention will be further described.
Embodiment 1
(1) synthesis of the compound N-ethyl-8-tertiary butyl-Isosorbide-5-Nitrae-dioxo spiro [4.5] decane-2-methylamine XI:
50 grams of methylsulfonic acid { 8-tertiary butyls-1 are added successively in 500 milliliters of autoclaves, 4-dioxo spiro [4.5] decane-2-methyl } ester X(0.163 mole), 21.9 gram of 67% ethylamine solution (0.326 mole) and 24.8 grams of salt of wormwood (0.179 mole), then 110-115 DEG C is heated to, internal pressure is that 0.4MPa stirring reaction is after 24 hours, reaction mixture distillation removing ethanol and excessive ethylamine solution recovery, residue adds 700 milliliters of ethylene dichloride and 300 ml waters, stratification after stirring and dissolving, organic layer concentrating under reduced pressure obtains 39.5 grams of brown liquid N-ethyl-8-tertiary butyls-1, 4-dioxo spiro [4.5] decane-2-methylamine XI, yield 94.9%.
1H NMR(400MHz,CDCl3)δ(ppm)4.20-4.30(m,1H),4.00-4.10(m,1H),3.6-3.7(m,1H),2.60-2.80(m,4H),1.80-1.90(m,1H),1.70-1.80(m,3H),1.60(m,1H),1.2-1.5(m,3H),1.1-1.2(m,3H),1.0-1.1(m,1H),0.90(s,9H)。
(2) synthesis of the compound N-ethyl-N-propyl group-8-tertiary butyl-Isosorbide-5-Nitrae-dioxo spiro [4.5] decane-2-methylamine (volution bacterium amine) I:
80 ml waters are added successively in 500 milliliters of autoclaves, 80 milliliters of ethylene dichloride, 14.0 grams of N-ethyl-8-tertiary butyls-1, 4-dioxo spiro [4.5] decane-2-methylamine XI(54.8 mmole), 8.33 grams of salt of wormwood (60.3 mmole), 0.88 gram of tributyl brometo de amonio (0.274 mmole) and 10.1 grams of positive propyl bromos (82.2 mmole), stirring is warming up to 115-118 DEG C and internal pressure is after 0.7MPa reacts 24 hours, reaction solution is chilled to room temperature, stratification, organic layer concentrating under reduced pressure obtains 15.4 grams of light yellow oil N-ethyl-N-propyl group-8-tertiary butyls-1, 4-dioxo spiro [4.5] decane-2-methylamine (volution bacterium amine), yield 95%:.
1H NMR(400MHz,CDCl3)δ(ppm)4.20(m,1H),4.00-4.10(m,1H),3.65(q,1H),2.40-2.70(m,6H),1.10-1.90(m,10H),1.00(m,4H),0.90(m,12H)。
Embodiment 2
(1) synthesis of compound N-propyl group-8-tertiary butyl-Isosorbide-5-Nitrae-dioxo spiro [4.5] decane-2-methylamine XII:
25.0 grams of methylsulfonic acid { 8-tertiary butyls-1 are added successively in 500 milliliters of autoclaves, 4-dioxo spiro [4.5] decane-2-methyl } ester X(81.6 mmole), 9.65 grams of Tri N-Propyl Amines (163.2 mmole), 12.4 grams of salt of wormwood (89.76 mmole) and 150 milliliters of ethanol, reaction mixture is heated to 110-115 DEG C and internal pressure is 0.5MPa, stir lower reaction and after 24 hours, be chilled to room temperature, reaction mixture distillation removing ethanol and excessive propylamine recovery, residue adds 500 milliliters of ethylene dichloride and 200 ml waters, stratification after stirring and dissolving, organic layer concentrating under reduced pressure obtains 17.6 grams of brown oil N-propyl group-8-tertiary butyls-1, 4-dioxo spiro [4.5] decane-2-methylamine XII, yield 80%.1H NMR(400MHz,CDCl3)δ(ppm)4.20-4.30(m,1H),4.01-4.06(m,1H),3.65-3.67(m,1H),2.70-2.74(m,2H),2.57-2.63(q,2H),1.10-1.90(m,10H),1.00(m,1H),0.90(m,3H),0.80-0.90(m,9H)。
(2) synthesis of the compound N-ethyl-N-propyl group-8-tertiary butyl-Isosorbide-5-Nitrae-dioxo spiro [4.5] decane-2-methylamine (volution bacterium amine) I:
17.6 grams of N-propyl group-8-tertiary butyls-1 are added successively in 500 milliliters of autoclaves, 4-dioxo spiro [4.5] decane-2-methylamine XII(65.323 mmole), 10.67 grams of monobromethanes (98.00 mmole), 9.93 grams of salt of wormwood (71.86 mmole) and 150 milliliters of ethanol, autoclave is heated to 115-120 DEG C and internal pressure is 0.7MPa, stirring reaction is after 24 hours, reaction mixture distillation removing ethanol and excessive monobromethane recovery, residue adds 400 milliliters of ethylene dichloride and 200 ml waters, stratification after stirring and dissolving, organic layer concentrating under reduced pressure obtains 17.3 grams of glassy yellow liquid, yield 89%, purity: 99%.
1H NMR(400MHz,CDCl3)δ(ppm)4.20(m,1H),4.00-4.10(m,1H),3.65(q,1H),2.40-2.70(m,6H),1.10-1.90(m,10H),1.00(m,4H),0.90(m,12H)。
Embodiment 3
(1) synthesis of compound N-propyl group-8-tertiary butyl-Isosorbide-5-Nitrae-dioxo spiro [4.5] decane-2-methylamine XII
31.2 grams of tosic acid { 8-tertiary butyls-1 are added successively in 500 milliliters of autoclaves, 4-dioxo spiro [4.5] decane-2-methyl } ester X ' (81.59 mmole), 14.47 grams of Tri N-Propyl Amines (244.76 mmole), 12.4 grams of salt of wormwood (89.75 mmole) and 150 milliliters of ethanol, 118-120 DEG C is heated in autoclave, internal pressure is 0.7MPa, stirring reaction is after 24 hours, , concentrating under reduced pressure reclaims ethanol and excessive Isopropylamine, residue adds 700 milliliters of ethylene dichloride and 500 ml waters, stir stratification, organic phase concentrating under reduced pressure obtains yellow oily liquid 21 grams of N-propyl group-8-tertiary butyls-1, 4-dioxo spiro [4.5] decane-2-methylamine XII, yield: 95.5%.
1H NMR(400MHz,CDCl3)δ(ppm)4.20-4.30(m,1H),4.01-4.06(m,1H),3.65-3.67(m,1H),2.70-2.74(m,2H),2.57-2.63(q,2H),1.10-1.90(m,10H),1.00(m,1H),0.90(m,3H),0.80-0.90(m,9H)。
(2) compound N-ethyl-N-propyl group-8-tertiary butyl-Isosorbide-5-Nitrae-dioxo spiro [4.5] decane-2-methylamine (volution bacterium amine) I synthesizes:
The 20.0 g of compound N-propyl group-8-tertiary butyls-1 are added successively in 500 milliliters of autoclaves, 4-dioxo spiro [4.5] decane-2-methylamine XII(74.23 mmole), 12.13 grams of monobromethanes (111.35 mmole), 11.3 grams of salt of wormwood (81.65 mmole) and 150 milliliters of ethanol, 80 DEG C are heated in autoclave, , internal pressure is 0.4MPa, stirring reaction is after 24 hours, , concentrating under reduced pressure reclaims ethanol and excessive monobromethane, residue adds 400 milliliters of ethylene dichloride and 200 ml waters, stir stratification, organic phase concentrating under reduced pressure obtains the light yellow oil 15.5 g of compound N-ethyl-N-propyl group-8-tertiary butyl-1, 4-dioxo spiro [4.5] decane-2-methylamine (volution bacterium amine) I, yield 70%, purity: 97%.
1H NMR(400MHz,CDCl3)δ(ppm)4.20(m,1H),4.00-4.10(m,1H),3.65(q,1H),2.40-2.70(m,6H),1.10-1.90(m,10H),1.00(m,4H),0.90(m,12H)。
Claims (18)
1. a synthetic method for sterilant volution bacterium amine, is characterized in that comprising the steps:
(1) compounds X reacts in sealing system with alkylamine under alkali effect under temperature 80 ~ 150 DEG C, pressure 0.1 ~ 1.0MPa, obtains compounds X I;
(2) compounds X I and alkyl bromide and alkali carry out being obtained by reacting Compound I in temperature 40 ~ 200 DEG C, pressure 0.1 ~ 1.0MPa under phase-transfer catalyst effect in sealing system;
Its reaction equation is as follows:
Wherein, R
1for C
1 ~ 4alkyl or C
1 ~ 4alkyl phenyl; R
2for n-propyl or ethyl.
2. synthetic method according to claim 1, is characterized in that described R
1for methyl or 4-aminomethyl phenyl.
3. synthetic method according to claim 1, it is characterized in that in step (1), described alkali is salt of wormwood, and described alkylamine is ethamine, Tri N-Propyl Amine, ethylamine solution or the Tri N-Propyl Amine aqueous solution, and the mass concentration of ethylamine solution or the Tri N-Propyl Amine aqueous solution is 50 ~ 80%.
4. synthetic method according to claim 3, is characterized in that in step (1), and the mass concentration of ethylamine solution or the Tri N-Propyl Amine aqueous solution is 50 ~ 60%.
5. synthetic method according to claim 1, is characterized in that in step (1), and the mol ratio of compounds X and alkylamine and alkali is 1.0:1.5 ~ 10:1.0 ~ 3.0.
6. synthetic method according to claim 5, is characterized in that in step (1), and the mol ratio of compounds X and alkylamine and alkali is 1.0:2.0 ~ 3.0:1.05 ~ 1.2.
7. synthetic method according to claim 1, is characterized in that in step (1), and reaction solvent is that ethanol is or/and water.
8. synthetic method according to claim 7, is characterized in that, in step (1), temperature of reaction is 80 ~ 120 DEG C.
9. synthetic method according to claim 1, it is characterized in that, in step (1), reacting and carrying out in sealing system, reaction pressure is 0.3 ~ 0.8MPa.
10. synthetic method according to claim 1, is characterized in that, in step (2), described alkyl bromide is positive propyl bromo or monobromoethane; Described alkali is salt of wormwood.
11. synthetic methods according to claim 1, it is characterized in that, in step (2), described phase-transfer catalyst is benzyltriethylammoinium chloride, Tetrabutyl amonium bromide, tetrabutylammonium chloride, 4-butyl ammonium hydrogen sulfate, tri-n-octyl methyl ammonium chloride, Dodecyl trimethyl ammonium chloride or tetradecyl trimethyl ammonium chloride.
12. synthetic methods according to claim 11, is characterized in that, in step (2), described phase-transfer catalyst is tributyl brometo de amonio.
13. synthetic methods according to claim 1, is characterized in that in step (2), and the mol ratio of compounds X I and alkali and alkyl bromide is 1.0:1.0 ~ 1.5:1.2 ~ 3.0.
14. synthetic methods according to claim 13, is characterized in that in step (2), and the mol ratio of compounds X I and alkali and alkyl bromide is 1.0:1.05 ~ 1.2:1.2 ~ 1.5.
15. synthetic methods according to claim 1, is characterized in that, in step (2), temperature of reaction is 80 ~ 130 DEG C.
16. synthetic methods according to claim 1, it is characterized in that, in step (2), reacting and carrying out in sealing system, reaction pressure is 0.3 ~ 0.8MPa.
17. synthetic methods according to claim 1, is characterized in that in step (2), and reaction solvent is nonhomogeneous system or the ethanol of water and organic solvent composition.
18. synthetic methods according to claim 17, is characterized in that in step (2), and reaction solvent is water and ethylene dichloride mixed solvent or ethanol.
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| CN105918335B (en) * | 2016-05-20 | 2018-09-07 | 南京华洲药业有限公司 | A kind of bactericidal composition and its application containing volution bacterium amine and Propamocarb |
| CN112409321B (en) * | 2019-08-22 | 2022-04-01 | 新发药业有限公司 | Method for preparing spiroxamine |
| CN112125878B (en) * | 2020-09-28 | 2024-01-02 | 陕西恒润化学工业有限公司 | Spiroxamine and synthesis method thereof |
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| DE19529090A1 (en) * | 1995-08-08 | 1997-02-13 | Bayer Ag | Ethyl-propylamine prodn. used in agrochemicals prodn. - by reacting ethylamine with propionaldehyde in water-immiscible diluent, and catalytic hydrogenation of imine prod. |
| DE19956095A1 (en) * | 1999-11-22 | 2001-05-23 | Bayer Ag | Synergistic plant fungicide composition containing spiroxamine, tebuconazole and quinoxyfen, especially effective against cereal diseases |
| CN101822251A (en) * | 2010-01-27 | 2010-09-08 | 深圳诺普信农化股份有限公司 | Sterilization compound containing ZJ0712 |
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Non-Patent Citations (1)
| Title |
|---|
| Assignment of the Stereochemistry of Spiroxamine by Two-Dimensional NMR Spectroscopy and Stereoselective Chemical Synthesis;W. A. Etzel et.al.;《MAGNETIC RESONANCE IN CHEMISTRY》;19981231;第36卷;第65页scheme 2 * |
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Address after: No. 309 Changfeng River Road, Nanjing Chemical Industrial Park, Liuhe District, Nanjing, Jiangsu Patentee after: Jiangsu Zhongqi Polytron Technologies Inc Address before: No. 309 Changfeng River Road, Nanjing Chemical Industrial Park, Liuhe District, Nanjing, Jiangsu Patentee before: Jiangsu Flag Chemical Industry Co., Ltd. |