CN103058918A

CN103058918A - Method for synthesizing 2-chlorine-5-nitrapyrin and 2, 3-dichloro-5-nitrapyrin

Info

Publication number: CN103058918A
Application number: CN2012105050046A
Authority: CN
Inventors: 周景梅; 贺书泽; 丁泽升; 丁剑剑; 孙希祥; 张可; 卜标; 尹卫东
Original assignee: Jiangsu Yangnong Chemical Co Ltd
Current assignee: Jiangsu Youjia Chemistry Co., Ltd.; Jiangsu Yangnong Chemical Co Ltd
Priority date: 2012-11-30
Filing date: 2012-11-30
Publication date: 2013-04-24
Anticipated expiration: 2032-11-30
Also published as: CN103058918B

Abstract

The invention provides a synthesis technology for synthesizing 2-chlorine-5-nitrapyrin and 2, 3-dichloro-5-nitrapyrin. The synthesis technology specifically comprises the following steps of: with 2-chlorine-5-methylpyridine as a raw material, sequentially adding compounds of molybdenum or tungsten, namely a catalyst A and a catalyst B which are free radical reaction initiators, for chlorinated synthesis reaction, wherein the total weight for the added catalyst A and catalyst B is 0.01-2% of the feeding weight of 2-chlorine-5-methylpyridine; and adjusting the weight ratio of the catalyst A to the catalyst B in a range of 0.5-100:0, to obtain the mixture of 2-chlorine-5-nitrapyrin and 2, 3-dichloro-5-nitrapyrin in any proportion. According to the method, the mixture of 2-chlorine-5-nitrapyrin and 2, 3-dichloro-5-nitrapyrin in any proportion can be obtained by adjusting the proportion of the catalyst A to the catalyst B, so that arbitrary adjustment of the proportion of the obtained two products on one set of device can be realized.

Description

The method of synthetic 2-chloro-5-trichloromethylpyridine and two kinds of products of 2,3-, two chloro-5-trichloromethylpyridines

Technical field

The present invention relates to the synthetic method of 2-chloro-5-trichloromethylpyridine and two kinds of products of 2,3-, two chloro-5-trichloromethylpyridines.

Background technology

2,3-two chloro-5-trichloromethylpyridines and 2-chloro-5-trichloromethylpyridine are two important agricultural chemicals synthetic intermediates, wherein 2, and 3-two chloro-5-trichloromethylpyridines can further be fluoridized and obtain 2,3-two chloro-5-trifluoromethylpyridines, the latter is a kind of intermediate important in the fluoro nitrogen heterocycles agricultural chemicals, by its synthetic agricultural chemicals one class such as fluazifop, and the spirit of chlorine fluorine second standing grain, the weedicides such as haloxyfop, it is high that they have drug effect, and toxicity is low, pollutes the characteristics such as little; Another kind of such as process for preparation of benzoylurea compounds such as fluorine pyridine ureas, the mechanism of action is unique, has efficient, low toxicity, the distinguishing feature such as environmentally friendly; And the 2-chloro-5-trichloromethylpyridine is fluoridized the crucial mesosome that the 2-chloro-5-trifluoromethylpyridine that obtains is new herbicides agricultural chemicals fluazifop-p-butyl, the synthesis technique of two kinds of intermediates is similar, but traditional synthesis method is owing to using the difference of raw material and catalyzer, technological process also has difference, present invention focuses on by a covering device, one kettle way synthesizes these two kinds of products, only adjusts arbitrarily the ratio of two kinds of products in the process according to the ratio that adds two kinds of catalyzer.

Summary of the invention

The object of the invention provides a cover 2-chloro-5-trichloromethylpyridine and 2, the synthesis technique of two kinds of products of 3-two chloro-5-trichloromethylpyridines, and any adjustment that realizes two kinds of product proportions that is adjusted on the covering device by the catalyst combination ratio, the building-up reactions formula is as follows:

Possess and may further comprise the steps: take the raw material CMP as raw material, the compound that adds successively free radical reaction class of initiators catalyst A and another kind of catalyst B molybdenum or tungsten, carry out the chlorination building-up reactions, the gross weight that two kinds of catalyzer of described A, B add accounts for CMP 0.01%～2% of the weight that feeds intake; By adjusting the weight ratio of described catalyst A and catalyst B in the scope between 0:5～100:0, obtain the mixture of 2-chloro-5-trichloromethylpyridine and two kinds of product arbitrary proportions of 2,3-, two chloro-5-trichloromethylpyridines.

In the inventive method, the preferred Diisopropyl azodicarboxylate of described catalyst A or benzoyl peroxide free radical reaction initiator.

In the inventive method, muriate or the oxide compound of the preferred molybdenum of described catalyst B or tungsten.

In the solution of the present invention, the further preferred molybdenum pentachloride of described catalyst B or tungsten hexachloride.

In the preferred scheme of the present invention, the weight ratio of described catalyst A and B is preferably adjusted in the scope of 1:3.2～110:6; Further preferably in the scope of 1.05:3～100:7, adjust.

Among the present invention, because additional proportion and 2-chloro-5-trichloromethylpyridine and 2 of A, two kinds of catalyzer of B, there is corresponding relation in the proportion of composing of 3-two chloro-5-trichloromethylpyridines two products, therefore, by adjusting the ratio between catalyst A and the B, the mixture of 2-chloro-5-trichloromethylpyridine and 2,3-, two chloro-5-trichloromethylpyridines, two product arbitrary proportions can be accessed, any adjustment of two kinds of product proportions obtaining at a covering device can be realized thus.

Embodiment

In following examples, except special stipulation, described product proportion is mol ratio.

Embodiment 1:

Drop into CMP 100g, intensification 140-150 degree adds then logical chlorine reaction of catalyzer Diisopropyl azodicarboxylate 0.100g, and add catalyzer molybdenum pentachloride 0.030g after 10 hours and continued again 5 hours, middle control, the ratio of two kinds of products is 5:5 approximately.

Embodiment 2:

Drop into CMP 100g, intensification 140-150 degree, add then logical chlorine reaction of catalyzer Diisopropyl azodicarboxylate 1.0g, adding catalyzer molybdenum pentachloride 0.5g after 10 hours continued 5 hours again, middle control, the ratio of 2-chloro-5-trichloromethylpyridine and 2,3-, two chloro-5-trichloromethylpyridines is 4:6 approximately.

Embodiment 3:

Drop into CMP 100g, intensification 140-150 degree, add then logical chlorine reaction of catalyzer Diisopropyl azodicarboxylate 0.100g, adding catalyzer molybdenum pentachloride 0.130g after 10 hours continued 5 hours again, middle control, the ratio of 2-chloro-5-trichloromethylpyridine and 2,3-, two chloro-5-trichloromethylpyridines is 2:8 approximately.

Embodiment 4:

Drop into CMP 100g, intensification 140-150 degree, add then logical chlorine reaction of catalyzer Diisopropyl azodicarboxylate 0.100g, adding catalyzer molybdenum pentachloride 0.300g after 10 hours continued 5 hours again, middle control, the ratio of 2-chloro-5-trichloromethylpyridine and 2,3-, two chloro-5-trichloromethylpyridines is 1:9 approximately.

Embodiment 5:

Drop into CMP 100g, be warmed up to the 140-150 degree, add then logical chlorine reaction of catalyzer benzoyl peroxide 0.0105g, adding catalyzer tungsten hexachloride 0.0315g after 10 hours continued 5 hours again, middle control, the ratio of 2-chloro-5-trichloromethylpyridine and 2,3-, two chloro-5-trichloromethylpyridine products is 1:9 approximately.

Embodiment 6:

Drop into CMP 100g, be warmed up to the 140-150 degree, add then logical chlorine reaction of catalyzer benzoyl peroxide 0.105g, adding catalyzer tungsten hexachloride 0.140g after 10 hours continued 5 hours again, middle control, the ratio of 2-chloro-5-trichloromethylpyridine and 2,3-, two chloro-5-trichloromethylpyridine products is 2:8 approximately.

Embodiment 7:

Drop into CMP 100g, be warmed up to the 140-150 degree, add then logical chlorine reaction of catalyzer benzoyl peroxide 0.105g, adding catalyst oxidation tungsten 0.053g after 10 hours continued 5 hours again, middle control, the ratio of 2-chloro-5-trichloromethylpyridine and 2,3-, two chloro-5-trichloromethylpyridine products is 3:7 approximately.

The method of other embodiments of the invention and above-described embodiment 1-7 is basic identical, and wherein catalyzer add-on and the group of products corresponding relation between proportional is shown in Table 1.Wherein, A1 represents Diisopropyl azodicarboxylate, and A2 represents benzoyl peroxide; B1 represents molybdenum pentachloride, and B2 represents tungsten hexachloride; A represents the 2-chloro-5-trifluoromethylpyridine, and b represents 2,3-, two chloro-5-trifluoromethylpyridines.

Table 1

Embodiment	A1（g）	B1（g）	A2（g）	B2（g）	a	b
							8	0.1	0.08	?	?	30	70
9	0.1	0.024	?	?	60	40
							10	0.1	0.018	?	?	70	30
11	0.1	0.012	?	?	80	20
							12	0.1	0.006	?	?	90	10
13	?	0.3	0.105	?	10	90
							14	?	0.13	0.105	?	20	80
15	?	0.08	0.105	?	30	70
							16	?	0.05	0.105	?	40	60
17	?	0.03	0.105	?	50	50
							18	?	0.024	0.105	?	60	40
19	?	0.018	0.105	?	70	30
							20	?	0.012	0.105	?	80	20
21	?	0.006	0.105	?	90	10
							22	0.1	?	?	0.31	10	90
23	0.1	?	?	0.134	20	80

[0029]?

24	0.1	?	?	0.083	30	70
							25	0.1	?	?	0.052	40	60
26	0.1	?	?	0.034	50	50
							27	0.1	?	?	0.027	60	40
28	0.1	?	?	0.02	70	30
							29	0.1	?	?	0.014	80	20
30	0.1	?	?	0.007	90	10
							31	?	?	0.105	0.084	30	70
32	?	?	0.105	0.035	50	50
							33	?	?	0.105	0.028	60	40
34	?	?	0.105	0.021	70	30
							35	?	?	0.105	0.014	80	20
36	?	?	0.105	0.007	90	10

Claims

1.2-chloro-5-trichloromethylpyridine and 2, the synthesis technique of two kinds of products of 3-two chloro-5-trichloromethylpyridines, it is characterized in that, possess and may further comprise the steps: take the raw material CMP as raw material, the compound that adds successively free radical reaction class of initiators catalyst A and another kind of catalyst B molybdenum or tungsten, carry out the chlorination building-up reactions, the gross weight that two kinds of catalyzer of described A, B add accounts for CMP 0.01% ~ 2% of the weight that feeds intake; By adjusting the weight ratio of described catalyst A and catalyst B in the scope between 0:5 ~ 100:0, obtain the mixture of 2-chloro-5-trichloromethylpyridine and two kinds of product arbitrary proportions of 2,3-, two chloro-5-trichloromethylpyridines.

2. method claimed in claim 1, it is characterized in that: described catalyst A is selected in Diisopropyl azodicarboxylate or benzoyl peroxide free radical reaction initiator.

3. method claimed in claim 1, it is characterized in that: described catalyst B is selected in the muriate of molybdenum or tungsten or oxide compound.

4. method claimed in claim 3, it is characterized in that: described catalyst B is selected in molybdenum pentachloride or tungsten hexachloride.

5. method claimed in claim 1, it is characterized in that: the weight ratio of described catalyst A and B is adjusted in the scope of 1:3.2 ~ 110:6.

6. method claimed in claim 1, it is characterized in that: the weight ratio of described catalyst A and B is adjusted in the scope of 1.05:3 ~ 100:7.