Dimethomorph is a morpholine-based fungicide developed by Shell (now BASF), which is widely used in various regions of the world and has been the top morpholine-based fungicide in global sales in recent years. It is used for the control of vegetable downy mildew, blight, seedling blight, tobacco black tibia and other diseases caused by oomycetes of the subphylum Flagellomycetes, and has systemic activity. Without considering the resistance of pathogenic fungi, it is more effective than mefenoxam, fenoxycarb, aluminum triethionate and oxamyl, which are widely used at present.
1 Biological activity of enoylmorpholine
1.1 Biological activity of enoylmorpholine single agent
The indoor virulence determination of 20% enoylmorpholine SC showed that: 20% enoylmorpholine SC had good growth inhibition of Botrytis cinerea, and the pathogenicity and sporulation ability of the pathogenic bacteria decreased after the agent treatment, and the parasitic fitness index also decreased with the increase of the mass concentration of the liquid.
The average efficacy of 10% enoylmorpholine EW 600 mL/hm2 against grapevine downy mildew at 14 d after two applications was 84.6%, which was significantly better than 25% methomyl WP 900 g/hm2; the efficacy of 225.0, 262.5 and 300.0 g/hm2 against cucumber downy mildew was 75.32%, 82.79% and 88.77%, respectively. 50% enoylmorpholine WP 600g/hm2 has obvious effect on cucumber downy mildew. 80% enoylmorpholine WG 228-300 g a.i./hm2 with 3 applications can effectively control cucumber downy mildew with 75.77%-78.44%, and it is safe for cucumber. 40% enoylmorpholine WG 1,000-1,500 times in the small fruiting period, middle fruiting period and fruit ripening period of lychee. It can effectively control the damage of litchi fungal mildew by applying one application each in the middle and ripening period.
The EC50 values were 0.68, 0.21 and 4.92 mg/L, respectively, and the activity was 34.7, 30.4 and 4.6 times higher than that of pyrimethanil. The effectiveness of enoylmorph against pepper blight was 66% better than that of pyrimethanil when treated with a spray solution of 800 mg/L 24 h after inoculation of pepper plants. The effectiveness of enoylmorph against pepper blight was 73.89%, 83.33% and 86.67% at 150, 225 and 300 g a.i./hm2, respectively.
1.2 Biological activity of the enoylmorpholine mixture
According to the literature, enoylmorpholine has good control effect when mixed with daidzein, thiram, chlorothalonil and methomyl, and the compounded formulations showed synergistic effect. The use of enoylmorpholine compounded formulations enhances the protective and therapeutic effects of pharmaceuticals, expands the fungicidal spectrum and delays the resistance of pharmaceuticals.
The efficacy of 69% dexamethane-enoylmorpholine WP against cucumber downy mildew ranged from 62.90% to 70.67% after 1 application for 7 d, and 73.53% to 83.19% after 2 applications for 7 d, both of which were significantly higher than that of the single agent. 69% dexamethane-enoylmorpholine WP 1,999.5 g/hm2 had an efficacy of 87.4% for 7 d and 84.5% for 14 d after application against cucumber downy mildew. The efficacy of 69% enoylmorpholine-dextran WP 1,242 and 1,553 g/hm2 against cucumber downy mildew at 7 d after two applications reached 76.1% and 78.2%, respectively, and the equivalent cucumber yield was 10.7% and 10.2% higher than that of the single agent, which were better than that of the single agent.
The efficacy of 50% fumioxazin-allylmorpholine WP 750 g a.i./hm2 against cucumber downy mildew was 76.5%. 55% fumioxazin-allylmorpholine WP 2,400 g/hm2 against cucumber downy mildew was 74.19%. 69% fumioxazin-allylmorpholine WP against cucumber downy mildew in protected and open field was tested, and the efficacy of 1,242 g a.i./hm2 after 3 applications for 7 d was 85.98%. The control efficacy of 1,242 g a.i./hm2 was 85.98% and 90.26%, respectively, which was significantly higher than that of the control agent 50% allylmorpholine WP 262.5 g a.i./hm2 and 50% fomesin WP 1,350 g a.i./hm2.
The results of the indoor pot trials showed that the dose required for the therapeutic effect of 56% copper hydroxide-enoylmorpholine WP on pepper blight was about twice the dose required for the protective effect. The results of field test showed that the relative efficacy of 56% copper hydroxide-enoylmorpholine WP 280.0mg/L was more than 90.32% in the growth period and more than 75% in the fruiting period with two doses.
The relative efficacy of 50% enoylmorpholine WG 1,000 times with 3-4 applications at 5-6d interval was better than that of 64% fomesane-manganese WP 1,125, 2,250 g/hm2 and the efficacy of 10d after 3 applications was 84.53% and 85.79% against taro blight respectively, both of which were better than that of 64% fomesane-manganese WP 1,500 The efficacy was better than 64% manganese zinc WP 1,500 g/hm2, 90% aluminum triethionate SP 1,500 g/hm2, 25% methomyl WP 1,500 g/hm2.
2 Foreign market status of enoylmorpholine
Allylmorpholine is a morpholine-based product developed by Shell, which entered the market in 1992. The product has belonged to Shell, Cyanamid and BASF successively with the transfer and acquisition of the company. After entering the market, enoylmorpholine was developed and has a certain market coverage. Most of the morpholine-based fungicides for the control of powdery mildew (Erysiphe graminis), and enoylmorpholine, despite being a morpholine-based fungicide, is by directly destroying the formation of fungal cells, causing the decomposition of the cell wall, thus causing the death of fungal cells, which does not have the effect of controlling powdery mildew. Used to control potato, grape, cucurbit downy mildew, and for tomato and other crop diseases. Allylmorpholine alone has a high risk of resistance, so it is often used in combination with protective fungicides such as daidzein to delay the development of resistance.
In 2002, it was further registered in the U.S. and re-registered in the EU. 2007, it was successfully re-registered in the EU Annex 1 list. Currently the main market for enoylmorpholine is in Europe, followed by Asia.
The main varieties for disease control are benzamide compounds such as methomyl, oxamyl and benomyl. However resistance has become a problem and these products are now only recommended for mixing with other classes of pesticides in the early stages of the disease. Fenoxycarb is also widely used for blight control, usually in blends with pyrimethanil. As research on oomycete fungicides has intensified (including potato blight), recently introduced products (including those in late stages of development) have shown significant advances in blight control. These include allylmorph, which is the first product to target oomycete diseases, and the growth in the use of allylmorph has led to growth in disease fungicides.
Sales of allylmorph began to decline after 2002 as more oomycete products entered the market and became more competitive. 2007 and 2008 saw a slight increase in sales of allylmorph, followed by a decline in sales in 2009. The fungicide market, which is dominated by potatoes, declined by 7.5% to 124,000 hm2 in 2008-2009, and the fungicide market declined by 3% to $32 million, which was also a reason for the decline in sales of enoylmorph. France is a major market for grape fungicides, with a market value of $250 million in 2009, down 12% from 2008. Products used to control downy mildew on grapes, which generally account for 60% of the market, were affected by the long winter and large inventories, resulting in lower product prices, which was also a factor in the decline in sales of enoylmorpholine. Germany’s grape acreage has remained relatively stable over the years, with grape fungicide sales of €34 million in 2009, up 25.9% from 2008, and a 5.4% increase in grape fungicide acreage, which was a favorable factor in the growth of sales of enoylmorpholine products. 2010 sales of enoylmorpholine were $80 million, compared to $85 million in 2009 and $95 million in 2008. Sales in 2008 were $95 million.
3 Enoylmorpholine Domestic Market Status
As of November 3, 2011, the total number of unexpired registrations for enoylmorpholine is 114. Among them, there were 2 registrations in 2007, 21 registrations in 2008, 30 registrations in 2009, 8 registrations in 2010 and 53 registrations in 2011. The number of registrations has been increasing year by year. Ltd., BASF Europe, Anhui Fengle Agrochemical Co., Ltd., Jiangsu Weinong Chemical Co. Ltd. and Jiangsu Huifeng Agrochemical Co.
The crops and control objects of enoylmorpholine registered in China are cucumber downy mildew, potato late blight, grape downy mildew, tobacco black tibia, pepper blight, tomato late blight, melon downy mildew, kale downy mildew, potato early blight.
Allylmorph is registered with manganese zinc, fomesin, methomyl, aluminum triethionate, chlorothalonil, zinc propoxur, fenoxycarb, pyraclofenoxuron, copper turpentine. The registered dosage forms of enoylmorpholine are wettable powder, water dispersible granule, water emulsion, suspension, microemulsion, effervescent tablet and fumigant.
The first registration of enoylmorpholine in China was in 2002 by Shandong Xianda Chemical (Group) Co. At that time, the market volume of enoylmorpholine is very small, belonging to the latest agents for the control of downy mildew and epidemics. Immediately after the domestic production of 8 to 10 enterprises of the product, the domestic market was quickly developed, the use of a substantial increase, is now the largest use of downy mildew, epidemic agents. Ltd., Jiangsu Changlong Chemical Co., Ltd., Jiangsu Cultivation Chemical Co., Ltd., the output is shown in Table 1.
Table 1 The main manufacturers and production of enoylmorpholine (t)
Manufacturers
2011
2010
2009
2008
Germany BASF
300
300
300
300
Shandong Xianda
500
250
230
200
Jiangsu Changlong
200
400
300
300
Jiangsu Cultivation
200
300
200
200
The capacity of the domestic market is about 500~600t, and the export is 200~300t/year, mainly to Southeast Asia, South America and other regions.
At present, the domestic market is already saturated and the patent of international market has just expired. The international market is mainly dominated by BASF products. However, the output of BASF is only 300t, and the production plant is in Brazil. Since the price of domestic products is lower than their production cost, there is a certain competitiveness. With the opening of the international market, the market prospect of domestic products is relatively broad. The main markets of enoylmorpholine in the international are Brazil, the United States, Europe, Australia and other developed countries, mainly used in grapes. The total future global market usage of enoylmorpholine is 2,000~3,000t. With the registration of domestic enterprises’ products in the main global markets, the international market will be opened gradually in recent years.
