Document JJGNvMd6R7YK63bj0rEwRXzzO

AGRICULTURAL DIVISION CROP PROTECTION BUSINESS GROUP Research fc Development Department Monthly Summary - February, 1969 M. C. Throdahl Research A Development C. H. Alt D. D. Baird D. I. Biasing J. P. Cbupp t. A. Conkin V* A. Darlington J. M. iwaing J. S. Franz D. L. Gervltz P. C. Rasa L. H. Bannah G. R. Rarvey R. F. Rttatad I. G. Javorskl A. X. Lippaan G. f. Ludvlk G. J. Marco P. Perry C. A. Porter X. J. Prill X. W. Ratts V. R. Schrodt D. B. Sharp^""^ L. R. Ssith J. A. Stephens P. J* Stofiel C. C. Tung W. R. Udell X P. Upchurch V. B. Waldo C. L. Wilson Central Research Dept. B. L. Williams B. W. Mohraan B. J. Xdvards Patent Department ME Willia/FC Krlzov Medical Department X. X. Kelly DISTRIBUTION Agricultural Division International Division J. C. Barnett W. D. Carpenter 8. D. Daniels W. P. Dunlap P. B. Elliott DJ .. ft. W. Fischer Gillespie W. ft. Bayes P. F. Hoffman C. F. Luscke W. J. McCarvllle P. T. Mitchell C. B. Russell B. L. Payton M. L. Reding W. R. Robirds R. R. Ruaer P. L. Wright J. J. lanelk Technical Reports Library M. X. Madden Inorganic Division J. P. Bcrndt J. W. Tripp Organic Division F. B. Zienty 8. A. Helnlnger J J d 'A b i c o / hw K U b o u r n a T. M. Patrick W. X. Johnson MRC H. K. Mason X. W. Easley ' S. E. Hardy Washington, D.C. J. D. Early ,-MCL . J. W. Barrett R. A. Ritar B. MacDonald C. F. Calll* Plmstics/Resins Division R. J. Sehats Bydrocarbons/Polyaera Dlv. XC tallman/LJ Spillane Mev Enterprise Division X. 8. Gordon LK Klein/FC Meysr MCAL F. A. Nihil1 Monsanto Research 8.A. B. B. Zeiss Monsanto Europe R. P. Wilson Monsanto Japan D. T. Movry baiuoob AAtOCULTUHAI. D IV IS IO N CROP PROTECTION BUSINESS GROUP RESEARCH It DEVELOPMENT DEPARTMENT MONTHLY SUMMARY - FEBRUARY, 1969 i This document contains confidential Information which is ths property of Monsanto Company. Only those portions of tbs document relevant to a duly authorised Individual's need to know say be ex cerpted for his. This report aust not be sent outside the cospany without written approval, and the authorized recipient is accountable for its safekeeping, excerpting or otherwise disclosing of its contents and for the proper disposal of It. Please destroy this report when w ith" It.----- *-------- " ------- y1-o-u--a-r-e--f-i-n-i-s-h-e-d W 1S007 MONTHLY SUMMARY FEBRUARY, 1969 BJGRLIGHTS Chloracnegen Demonstration of the process amendment for reducing TDD formation in the Nltro 2,4,5-T plant as successful. Tim con tent of the four batches (2.3-4.3 ppa) as well below the 25-40 ppa usually found. Ramrod USDA questions regarding Atrazine BOV ingredients and Baarod/Atrazlne stability were resolved by laboratory test data. The physical mixture label was accepted by USDA on February IS, 1969 (USDA Registration No. 524-286) four and one-half sooths following submission of the data. lasso The lasso EC label was approved by the USDA on January 30, 1969 (USDA Registration Ho. 524-285). The new Ingredient state ment, including the addition of epichlorohydrin to our EC formul ation, was submitted on February 10 and does not interfere with the already approved label. A revised Lasso EC label was sub-r sitted to the USDA on February 11. The 10G label is still under review. The unusual work load in the USDA say delay acceptance of the 10G label until the end of March. The process for recovering unreicted methanol from Step III makes high operating rates at Muscatine possible without exceeding pollution limits into the Mississippi-River. CP 41*45 Data from Florida sugar cane trials show sucrose increases of economic end practical slgnlfl. nee and protection of sucrose concentrations during freezing weather. Change in Primary Herbicide Screen A major modification is underway. Many of ths herbaceous perennials sad hard-to-klll annual weeds from our secondary programs are being Included in our primary program. bjiaooh MONTHLY SUMMARY FEBRUARY, 1969 HERBICIDES 2.4.S-T The process amendment for reducing TDD formation during the manufacture of Na 2,4,5-trichlorophenoxlde has been demonstrated la the Nitro plant. Four autoclave batches were run under the nee conditions. TDD content of these (2.3-4.3 ppa) vis lover than that of control batches (11.5-14 ppa) and well below the 25-40 ppa usually found in production material. An extended plant run using the modified process has been scheduled by Manufacturing. The TDD content of T-Acid should drop signi ficantly after all cuirvul materials have been worked out of the system. Ramrod The Raarod/Linuron formulations, wettable powder made at Chapman and granular made at Muscatine, have been evaluated. Assays and physical properties are satisfactory. York to im prove the precision of the analytical control methods continues. In response to questions from USDA concerning the exact composition of the Ranrod/Atrazlne one-package mixture, the in gredients of Atrazlne 80V were identified by chemical and in strumental methods. This information and stability data ob tained from accelerated aging testa were'presented to USDA in support of our petition for label registration. Four and one-half months following the submission of data, Lhw Ramrod/Atrazine physical mixture label was accepted by the USDA on February IS, 1969 (USDA Registration Ho. 524286). In accepting the label, the USDA has requested additional test results from field experience., with this product on corn and sorghum. HD will get this data by fall. Hev labels for both Ramrod 20G and Ramrod Wettable Powder are still under review by USDA. Some additional data were sub mitted to the USDA on January 27, 1969 to support our requests for Increased rates of tank mixing of Ramrod with Atrazlne. A status check with the"USDA indicated that all efficacy reviews were completed as of February 15, and it now appears that March 1st would be a good target date for label acceptance. York has been resumed to develop s "compacted granular" Ranrod/Atrazlne formulation. Our latent experimental products, preparsd from tbs wsttsbls powders by compaction under preesures up to 3,000 psi, showed good dispersion end cold water suspensiblllty; however, the particles dusted excessively in the baiyoos 2 attrition test. It appears that even higher pressures and an adhesive vill be required to sake a product with the desired physical properties. Lasso A process has been developed for recovering unreacted methanol fros Step XXX of the Lasso operation. The recovered mater ial can be re-cycled without further treatsent. Besides the obvious econoolc aspects this modification makes it possible to operate the plant at high rates without exceeding tu luantl-- ties specified la the Xova permit on discharging methanol into the Mississippi Elver. Engineering has scheduled a project to implement the recommended process changes at the Muscatine plant. Large samples of two new Lasso formulations Lariat and Lasso 15G, were prepared In the pilot plant. These materials will ha aval 11tart hy WT> in tha 10tod fi*)rt p r o j m , Bealdue data for a variety of field-treated crops are being obtained for Lasso in pea, onions and lima beans In the U.3. and soybean and corn seed samples from Canada. These are limited samplings, but all show negligible residues of or less thsn 0.1 ppm. A tentative meeting has been net up for March 17-18 with the Canadian Department of Agriculture and Canadian FDA on our Lasso and Ramrod/Atrazine petitions. Me hope to obtain label approval by tbe end of March. These petitions request clear ances for: 1) Lasso, when used alone oncorn and soybeans, and as a' tank mix wltb Atrazine on corn, and with Lprox on soybeans; and 2) tank and physical mix of Ramrod and Atrazine for use on corn. The EC label approved by the VSDA on January 3^. 1008. The USDA objected to four minor weed species listed on Lhiw label, autl they have been deleted. On February 10, 1069 a new ingred**at atatement for Lasso SC was submitted to USDA. This new Ingredient statement In cluded the addition of epicblorohydrin to our formulation. Thin does not Interfere with tbe approved Lasso SC label. A revised Lssso EC label was submitted to USDA on February 11, 1060. This new label Includes additional weed species not previously acesptsd, methods for aerial application, tank mix ing with Atrazine and Lorox and provides for uses of this pro duct In liquid fertilizer. The Za b s o petition to establish tolerances for La s s o on cotton and peanuts Is still under review by the Food and Drug Administration. Our 00-day time limit for this petition is March 27, 1969. MiyOio 3 The L u i o 10G label la still under review. A corrected Ingredient statement was submitted to the USDA on February 6, 1969. The latest check with USDA revealed that this label Is in the final stages of efficacy review. The unreasonable delay In gaining acceptance of the Ldsso 10G label, according to the USDA, Is their unusual work load over the past few months. Our best estimate of the acceptance of the 10G label is about the last part of March. The synthesis program to exploit Lasso technology has been extended to include a study of the reactions of 2,6-dlethylM-mcthylcncanllloe (arosethine) with electrophiles. Several new derivatives have been prepared for screening.* Surprisingly, several electrophiles failed to react at all. Vork Is In progress .to establish the relationships between reactivity and electrophilleity. Hopefully, this will point the way to preparing new potential herbicides. **T" (R a n H o y T ) The petition to establish tolerances for trichlorobenzylchloride Is currently being roviewod by the FDA. USDA certi fied the efficacy of this product on February 13, 1969. Our 90-day time limit for thla petition terminates May 13, 1969. gome additional toxicology data on liver weights for rata were furnished to the FDA on February 19, 1969. Since the FDA bad raised a question with respect to Increased liver weights In rata, they asked to see the Individual "raw data" from our 90day rat study. Rogue Virtually all of the residue procedure studies carried out to date using rice plants treated with Rogue-i*C consist ently reveal only 60% recovery of 3,4-dlchlorohnillne-14C (DCA). The rewaining on-ha?f of the radioactivity is neither extrac table nor steam-distillable. Apparently, thla non-recoverable 14C lit iicrumbled aauiig natural products or is chemically bound or present as functionally modified DCA molecules Metabolism and residue methods are being 'eveloped to attempt to define the nature of this "non-recoverable" KC-tagged material. 3,6-plmethylanlllne The program to develop a process for manufacturing 2,6XMCA, the key raw material for CP 53323 and CP 52665, continues. A new fixed-bed tubular reactor was successfully operated ualng various catalysts and an smmonia/2,6-xylenol feed. Conversions up to 40% were attained; product quality has not yet been de fined. Additional catalysts will be screened and optimum oper ating conditions will be established as rapidly as possible. Miaou "H-forpyl Rogue*1 Several years ago, a Halted asount of work was done on tbe preparation of H-forayl-N-acylanllldes and N-fonaylcarbanilates. One of the former, HK-fonayl Rogue*', exhibited outstand ing activity as a contact herbicide; other coapounds were aoderately active. A recent re-examination of test data and struc ture-activity relationships indicated that related coapounds derived Xros poly-substituted anilines should be prepared for testing. This work Is In progress. Broadleaf field Progran Specific test progress vlth four acadesic cooperatore .(Oregon, Iova, How jersey. North Carolina) have been formulated and approved. The new coapounds which will be field tested are'actlve, pre-emergence, on broadleaf weeds: CP 59233, 1-C1cyclohexen-l-yl)-4-(o-fluorophenyD-l-methylurea, and CP hu&btl, l-(3-hydroxyphenyl)-7-(l-cyclohexen-l-yO-j-methylurma, tert- butylcarbamate. In addition, studies will be carried out- at St. Charles. Far East Field Progran During the first four nonths of 1969 additional pre-emer gence berbielde tests in India, tbe Philippines, Malaysia, Thai land and Ceylon have been scheduled vlth our new rice berbici- dal candidates. The coapounds are: CP 29036, benzyl octa- bydro-lH-azonlne-l-carbothiolate; CP 29037, benzyl hexahydro- azoclne-l-(2H)-carbothlolate; CP 56250, 2-chloro-H-(2-nethyl-6- n-propyl-l-cyclohexen-l-yl)-N-(2-ethoxyethyl)-acetaalde; and C p 57177, 2-chloro-N-(2,6-diaethyl-l-cyclohexen-l-yl)-N-(2-n- butoxyethy1)-acetamide. ._ These compounds will be compared to CP 53619, N-(butoxymethyl)--2-rhloro-2*,6*-dJethylpcet'ani 1idm, end other coapounds. Tbe results will be available by June 1, ltfbtf at wlilob Lime llie 1 9 Far Earnl mummer season program 'ill be planned. Primary Herbicide Screen Cha n t s To keep abreast of the changing meed control opportunities, l.e., those weed situations where products and aethoda are either Inadequate or non-existent, a major modification of our priaary herbicide screen la underway. The opportunity factor for success will be greetly improved by tbe change to a weed species spectrua which reflects unanswered weed control probleas. Among tbe newly Included key species are herbaceous perennials; nutsedgef quackgrase, johnsongrasa and Canada thistle; end annual weeds: velvetleaf, smartweed, eoeklebur and laabsquarter. All of theas weeds were part of our secondary programs in the past. b3iyoi ft national Ctnetr Institute - Kation! Institutes of Health A preliminary examination has been nade of the raw data supplied bj HCI-NXH from their studies "designed" to develop a screening tool for tuaorlgenic conpounds. Of Monsanto's agri cultural chemicals, only Avadex and various phenoxyacetlc deri vatives were Included In this program, and only Avadex was con nected with an alleged Increase In degree of tumor Incidence as compared with control nice. A statistical evaluation of these raw data Is to be nade by NCX-NXH. It appears likely that they will publish these results in 6Ge for. INSECTICIDES Corn Bootvorn Insecticide The raratMrtn/creoertt* granular formulation continues to be a promising candidate for controlling the western corn rootvora. A major problem* however, is aswocialvd with Lhis experi mental product, l.e., "how USDA/FDA approval can be obtained for the use of cxvoeote,a complex, ill-defined mixture?" No agricultural uses of this product are currently known to be approved. To circumvent this problem, other simpler stabilizer candidates are being screened as rapidly as possible In an effort to define one or more alternates in time for limited field trials in 1969. Although we had made an assumptiqn that unit activity against western corn rootworm (VCR) larvae was not a limiting factor in the field performance of parathlon, a comparison was made with the newer soil insecticides.to verify this point. These tests have shown that the assumption was correct. The order of unit activity ou VCR larvmw is parmthiou > Dylutulc > Landrln > HOCAP> fiux > Furadan. Parathlon is times mors toxic to VCR larvae than Furadan. Obviously unit acti vity against larvae does not correlate with field performance, and persistent activity In the soil can be decisive. These teat results on larvae do not correlate with adult topical test data which was published by Harold Ball In-Nebraska. Furadan was roughly 2.ft times sore active than parathlon on adult corn rootworm. In soil tssta we have found persistent activity with CP 56768, 3-lsopropyl-4-cyanopbenyl nathanesulfonate; CP 5B294, S-(-tolyl)-0-phenyl methylphoaphoDOdithioate; CP 59593, 3isopropylphenyl-N-laobutenyl-N-methylcarbamate; and CP 59665, 3-lsopropylpbenyl-N-(l-cyclohexen-l-yl)-N-methjlcarbamate. Granular formulations of these will be made and tested since granulation prolongs soil performance in Niran and Bux. e Life Cycle S c n t a The life cycle screen against mosquitoes Is now routine. Of 247 compounds tested, 31 did not kill any life stage of the Insect, but did prevent egg deposition. These results are encouraging because they point to Insect control by population suppression rather than by direct kill, and because the chemistry Is again a departure froe conventional insecticide chemistry. Sheep Blowfly Inacctlcldo Inconclusive field trlsls of our candidate blowfly insect icides, CP 53808, 0,0-dlethyl-S-(2,6-diethylphenylcarbamoyl)metbylphosphorodlthloate, and CP 55784, its dimethyl analog, in Australia last season were due to loe blowfly Infestation. Blowfly activity has now started to build up again In New South Tales following rains. Jetting trials at four new locations should have been started last week. PLANT GROWTH REGULATORS Antltranspirants Field plans have been finalized for evaluation of FGR-1 at all selected Market Development fields and St. Charles. The two corn varieties to be used represent a relatively short, early maturing type (Dekalb XL-45, 105-day) and a tall, full season type (Pioneer 3567, 120-day). Two double sets of corn plants have had foliar Rogue-1*C treatment, and "soil** application of S j S ^ d ^ '-tet-rar.MnroaTnbenzene-iaC, the Rogue soil metabolite. Mature corn grain is required for residue and metabolism war). fox* uae ul Euguu a plant growth regulator. Carbohydrate Enhancement .The final harvests hare been made on the Florida sugar cane ripening trials. CP 41845, N,N-bls-/~(dlhydroxypbosphinyl)aetbyl 7-glycine, and CP 41820, / "(dihydroxyphosphinyl)-methy 1_7lalno Placetlc acid, increased sucrose content of cane. The ehealcala were applied to 2 varieties of 11-sonth-old cane in 10 gallons/acre at rates of 4-1/2 lbs/acre for CP 41820 and 3, 4-1/2 and 6 lbs/acre for CP 41845. For both varieties and both chemicals, sucrose content increased significantly over controls. The gain-over controls varied from 7% after 7 weeks with CP 41820 on both varieties to 10% after 10 weeks with CP 41845 on the C.P. 50-28 variety of cane. b31U0H There v u do apparent significant differences between all three application rates. Neither chemical had any apparent ef fect on the cane tonnage as coopered with controls. The in creased sucrose at 7 weeks for CP 41820 and at 8 and 10 weeks for CP 41845 are considered of economical and practical importance. Vith CP 41845, yield was Increasing at 7 weeks after application when a severe freeze occurred. Slopes of the graphs Indicate that the rate of sucrose loss after the freeze was greater In the control than in the treated cane. This apparent capacity to maintain higher sucrose concentrations under adverse wwatlier conditions may be very important, nut only in Florida and Louisiana where freezing often is a problem, but in other cane areas of the world where natural ripening carried out with controlled drought nay be interrupted by rain with a resultant drop in sucrose content. Cane ripening trials are being carried out in Australia again during 1969. Cooperative work la being carried on through the Bureau of Sugar Experiment Stations and with Colonial Sugar Refining Company. The trials this year are exclusively with CP 41845 and are designed to establish ths optimum rate, time of application, performance on at least three major varieties and potential for preventing late season deterioration In sucrose concentration occurring after the peak of normal ripen ing. Soybean Physiology Tbs nitrite reductase enzyme assay was evaluated using young trlfollolate leaves from soybeans. Preliminary results indi cate the ratio of the nitrite to nitrate reductase is 10:1. This ratio is somewhat higher than .has been reported for these two enzyses In corn (2 or 3:1), but is substantially lower than the ratio found in isolated tobacco cells (40:1). An experi ment to mouiLor the nilrale uptake aa well as these two enzymes will be initiated in February using the Dare variety cf soybeans. Methyl Thlobutyric Acid Collaborative researen with Dr. Samuel Wlldaan, UCLA, resulted In development of a suitable isolation and assay media for studying photosyathesis in Isolated tobacco chloropiast. If this technique has general applicability, it would permit ns to eonduet evaluations oh Isolated Intact cbloroplasts from other plant species of mors direct Interest to the Agricultural Division, such as corn, soybeans, wheat and rice. The isolation of intact chloroplasts from plants other than spinach has been most difficult, and for that reason, most of the literature on photosynthetle measurements of isolated chloroplasts has bean conducted with spinach. The modification of isolation proce dures involves ths use of bovine serum mlbumin whlcb yields intact tobacco chloroplasts that evolve oxygen under illumina tion and Immediately stop when Illumination la cut off. Ve ware able to demonstrate with such chloroplasts that protein synthesis was stimulated approximately 200% when chloroplasts were illuminated compared with chloroplasts kept la the dark. saiaoij 6 It 1b hoped that the use of methyl thiobutyrlc acid In such a systea may be useful In establishing its role In protein syn thesis initiation. LONG RANGE PLANNING The Identification and evaluation of the technical limita tions to world crop production has been established as a prim ary approach to long range planning. The initial study will focus ou eoroi soybeans! wheat, rice and sorghum production. Steps have been taken to ewLabllwli the current production prac tices and to Identify the technical limitations. Evaluation of these limitations will ssslst in directing future programs toward products which will meet significant needs of worldwide commercial agriculture. In addition to Involvement of Uonsanto personnel, contacts have been made with USOA, AID, foundations, universities and private industry to aaxinlze the utilization of technical knowledge. The area of flower control was outlined to identify poten tial product areas. These Include: hybridization in grains and control of flowering in tree fruits (thinning, annual bear ing, dormancy), flower and fruit drop in soybeans and cotton (lint quality through limiting the flowering period), growth regulators in vegetablss and flowering control for vegetable quality. Although all these areas are not prime market targets, the phenomenon of flowering must first be assessed on a tech nological and scientific basis before proceeding with specific U S programs. i Contacts and specific individuals have been identified at Rockefeller Foundation and AID for future, in-depth discus sions on worldwide agriculture) needs. Rockefeller programs at the Rockefeller-Ford Institutes are'being reviewed to out line specific progress. The international Division has been requested to provide H D with agricultural production in each region aa well as answers to some specific questions n hybrid seed production. PAPERS PUBLISHED R. K. Howe. "N-Alkylanillnomethylenemalononltrlles. A Convenient Synthesis through A Variation and Detension of the Hoerwein Amide Acstal Reaction". J. Org. Chem. 34, 230 (1969). PATENTS D.S. 3,418,334. Process for the Preparation of Substi tuted Parabanlc Acids. P. J. Stoffel. V.S. 3,418,364. Pesticides. V. Mark. &J1S01B V ^ * -rW>-i-- - -i V.- -3' <" *,**/*&^ w, l Vs**2&= .S. 3,419,585. 4 '-Uetbylsulfonyl-3-phenylsalicylanllidos. J. D. Early and J. P. Cbupp. 8*3. 3,422,202* Insecticidal and Fungicidal Usa of NAryl Dltbiooxanldea. J. F. Olin. U.8. 3,423,200.. 2-Trlchlorooethylbenzoxazole Ab b Herbi cide. 0. Rolan. U.R. 3,42},898. Product and Process of Feedins Rvnlnp.nts Food Containing Ethoxylatod Alcohols to Prosote Growth. K. R. Ervin and C. J. llarco. A. J. Spciale