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_lJRGIA INSTITUTE OF TECHNOLOGY OFFICE Of l,;UN I 1'11-\\.. I "'LIIYIII•I"" 1 ''~ • ,...,. •• '· PROJECT Al>MINISTRATION LlATA SHEET

00 ORIGINAt D REVISION NO. --- roject No. A '34 3 0 GTRIK*=f DATE _....1...101.J..~J J-'-4+-/ ~Yk=--- Seheei/Lab _- __;t_~-~M..;...;s~· =~;..______roject Director: ·1ft· -~n9 /.... Wt.t. ponsor: Get _11 (Qr_o. Ve I cLo:sf a, 6-11- 'yr,e Agreement: na l\()e111 en I= d zd~d Jl/2 rjf;J.. ~ward Period: ~rom I lj+'ljf;J. To 3)30/Y::{ (Performance) ------(Reporut lponsor Amount: Total Estimated: S l;;J., yt? Funded: s__ I,....;J.=t-1 ...... Y __ i_3 ______I ,~-----~~~-2V~~--~---

~[)MINISTRATIVE DATA OCA Contact z;tn d a If. I$()(.J&l 411 ;( ff).(J I) Sponsor Technical Contact: 2) Sponsor Admin/Contractual Matters: M.s, LJ',d7L t:l//ot

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Defense Priority Rating: __fJ~l .... 11,..7...,£ ____ _ Military Security Classification: /] ()0 ( (or) Company/Industrial Proprietary: RESTRICTIONS See Attached __.,1)+-+-/ .. zu..::;... _____ Supplemental Information Sheet for Additional Requirements. I l'ravel: Foreign travel must have prior approval - Contact OCA in each case. Domestic travel requires sponsor

approval where total will excee~ greater of $500 or 125% of approved proposal budget category. Equipment: Title vests with 0 QO e 0(0 r;?p~cf_ ~ I

COPIES TO:

Research Administrative Network Research Security Services Research Communications (2) Research Property Management "'Aepnrb Coordinator (OCAL- Project F ile Accounting GTRI Other P•D Procurement/EES Supply Services · Library Other ------GEORGIA INSTITUTE Of ·.TECHNOLOGY OFFICE OF CONTRACT ADMINISTRATION SPONSORED PROJECT TERMINATION SHEET

. ·_ Project Title: Analysis of Berbici~e Material , . A-3430 . Project No: Dr. Tung L. Wu Project Director: , Sponsor: Griffin Corporation

Effective Termination Date: ___._3.,/-.30..,./~81(M3~------

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[!] Final Invoice axkelusi•f'&bi'iliiWN&I 0 Final Fiscal RePQrt 0 Final Report. of Inventions 0 Govt. Property Inventory & Related Certificate 0 Classified Material Certificate

[]~her ______

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COPIES TO: Administrative Coordinator E ES Public Relations (2) Research Property Management Computer Input Accounting Project !)J. Procurement/EES Supply Services Library ~her'M.< Final Report

ANALYSIS AND RESEARCH OF GRIFFIN LINURON PRODUCT

Tung L. Wu Energy and Materials Sciences Laboratory Engineering Experiment Station Georgia Institute of Technology Atlanta, Georgia 30332

Research Project Number A-3430

Project Officer Ms. Linda Elliot Griffin Corporation P.O. Box 1847 Valdosta, Georgia 31601 i.

Table of Contents

1. Product Chemistry Data

a. Product chemistry . . 1

b. Product assay .. 2

2. Description of Manufacturing Process

a. Raw material . . . .. 3

b. Step by step Description of Manufacturing Process . 3 c. Discussion of impurity formation . 4 3. Analytical Hethods and Data a. High performance liquid chromatography

(HPLC) . 5

b. Thin layer chromatograhy (TLC) ...... 14

c. Gas chromatography - mass spectrometry

(GC/MS) . 15 d. Combination of TLC & GC/MS . 24 4. Physical and Chemistry Properties

a. Physical properties . 27

b. Chemical properties . . 27 ii.

List of Tables

Table 1. Analytical Results of Technical Linuron Samples using HPLC . . . . 7 Table 2. RF values of TLC Analysis of the "B" Technical Linuron Product 14 Table 3. GC Run Conditions for Analysis of Technical Linuron 16 Table 4. Nass Spectrometer Run Conditions and Tuning. Report ...... 17 Table 5. List of Mass of TLC Fraction #4 25 Table 6. Library Search for TLC Fraction #4 . 26 iii.

List of Figures

Page Figure 1. Chromatogram of HPLC Analysis 9 a. "A" Technical Linuron (T0110682) 10 b. "B" Technical Li.nuron 11 c. "A" Technical Linuron (Tll02798) 12 d. "A" Technical Linuron (Tll02584) 13

e. II C" Kayaku Technical Linuron 14 Figure 2. Thin Layer Chromatogram of "B" Technical Linuron 14 Figure 3. ,Reconstructed Ion Chromatogram of Technical Linuron 19 a. "A" T0110682 19 b. "B" product 20

c. II B 11 Tll02798 21 d. "A" Tll02584 22

e. ' II C" product •· 23 iii.

List of Figures

Pp.ge

Figure 1. Chromatogram of HPLC Analysis 9

a. "A" Technical Linuron (T0110682) 10

b. "B" Technical Linuron 11

c. "A" Technical Linuron (Tll02798) 12

d. "A" Technical Linuron (Tll02584) 13

e. "C" Technical Linuron 14

Figure 2. Thin Layer Chromatogram of "B" Technical

Linuron .... 14

Figure 3. Reconstructed Ion Chromatogram of Technical

Linuron 19

a. "A" T0110682 19

b. II B" product 20

c. "B" Tll02798 21

d. "A" Tll02584 22

e. "C" product . 23 1. Product Chemistry Data

a. Product Chemistr~ - Linuron is the active ingredient of a herbicide which is conunercially available under several trade names, such as: Afalon (Hoechst) Hoe-2810 (Hoechst) Herbicide-326 (du·Pont) Lorox (duPont) Linuron is a substituted urea herbicide, the molecular fonnula, chemical nomenclature and structural formula are depicted below. Molecular formula CgH 10 ci 2N2o2 Chemical Nomenclature 3-(3J4-dichlorophenyl) -1-methoxY-l-methYl - urea H ./ OCH 3 Cl N- C- N Structural formula -@- Cl / I CH b '-.. 3 Substituted urea herbicides are generally synthesized by four different routes: (1) Reaction of isocyanate with at-nines, (2) Reaction of carbamic acid chlorides with amines, (3) Reaction of carbamic acid phenyl esters with amine, and (4) Transamination of ureas with amines. These synthetic routes are depicted below, where R1 , R2 are alkyl or phenyl groups. -2-

H H / (1) - C= 0 + R2-NH.L0 ~ R1-N-C-N 0" \ R2

H H H (2) R -N-c-Cl + RL~-NH ~ R -N-c-N-R0 + HCl 1 II 2 1 ll . ~ 0 0

H H H (3) R 1 -N:.:~-o- 0 + R2-NH 2 ---?>- R 1 -N-~-NR2 + 0 -OH 0 0

H H /H (4) R -N-~-NH 2 + R2 i~H 2 ~ R 1 -N-~-N, + . NH 3 o o R2

Specifically, "B" Technical Linuron is made according to the following scheme. H .. @ H / Cl -fo\-N == C = O+NH OH . NaOH> Cl ·-o-N- C-N, p 2 Cl / . lb OH Cl CH 0H H CH 3 Cl --!0\-- N-c _N ~ 3 (CH3)2S04 Cl p il " oc~ ~--...... _.NaOH 0 b. Product Assay: Typical analysis of "B" Technical Linuron is summarized in the following: Chemical Name Structural Formula Percent 3-(3,4-dichloro 95% phenyl)-1-methoxy- Cl -0 -~-~-N_,CH3 1-methyl urea C1 G 'oCH3 3,4-dichlorophenyl H H 0.3% hydroxy-urea Cl -0 -N-c-N/ Cl ~ 6 'OH bis-(3,4-dichloro phenyl) urea H H 1.8% Cl -0-N-c-N- @-Cl Cl / b , Cl -3-·

Chemic-al Name Structur.al Formula Percent 3-(3,4-dichloro H H phenyl) methoxy Cl ~0 -N-c-N-"' -urea c1 " S 'ocH3 Biuret HN-c-NH-c-NH 0.5% 2 II II 2 0 0 Methoxybiuret H HN-c-NH-c-N -0CH 0.2% 2 II ft 3 0 0 Inorganic salts & Acetone insolubles 0.5% Residual Solvent 0.5% 100% 2. Description of Manufacturing Process a. Raw Material: The starting materials and their sources for manufacturing "B" Technical Linuron are summarized below: Chemicals Sources (1) 3,4-dichlorophenylisocyanate Bayer (West Germany) (2) Hydroxylammonium sulfate BASF · (West Germany) (3) Dimethylsulfate Hoechst (West Germany) (4) Methanol Many sources b. Step by Step Description of Manufacturing Process: (1) Dissolve 82 parts hydroxylamine sulfate in 300 parts water by adding 100 parts solution of 40% strength sodium hydroxide -4-

(2) To the aqueous solution of hydroxylamine formed in the above step, a toluene solution of 3,4-dichlorophenylisocyanate (188 parts in 400 parts) is added with good stirring and external cooling. (3) After completion of the addition, the mixture is stirred at 25°-30°C for 1 hour. The pre

cipitate of 3-(3,4-dichlorophenyl)~l-hydroxyurea is filtered and washed with water and dried. (4) 400 parts methanol are added to the dried 3-(3,4-dichlorophenyl)-1-hydroxyurea with stirring. Subsequently, 190 parts dimethylsulfate are also added. (5) 320 parts of 25% sodium hydroxide solution is slowly added to the reaction mixture. The reaction vessel is maintained at temperature between 10 to 20°C with external cooling. (6) The mixture is stirred for 1/2 hour, then 400 parts water are added to precipitate Linuron (3-(3,4-dichlorophenyl)-1-methoxy-1- methylurea). (7) Linuron is filtered, washed and dried. c. Discussion of Impurity Fomation: Since 3,4-dichlorophenyl hydroxyurea is the intemediate -5- material in the manufacturing of Linuron, small parts of 3,4-dichlorophenyl hydroxyurea remains in the Technical Linuron product as impurity. Two major impurities are formed, however, in the methylation process of the reaction inter- mediate, 0,4-dichlorophenyl hydroxyurea). 3-(3,4-dichlorophenyl) methoxyurea is resulted from incomplete methylation, while bis-(3,4-dichlorophenyl) urea is formed when two mole cules of 3,4-dichlorophenyl hydroxyurea react. 3. Analytical Methods and Data Five samples of Technical Linuron were provided by the Griffin Corporation, and were analyzed for Linuron and impurities. Technical Linuron samples were dissolved in Methanol and analyzed with the following four analytical methods. a. High Performance Liquid Chromatography (HPLC) Instrument: Micrometric Model 7000 High Performance Liquid Chromatograph Column: Microsil Cl8 Micrometric packing Solvent System: Isocratic mode 10/o isopropanol 90% isooctane Run Mode: Constant pressure (1900psi) Flow Rate approximately 1.7 ml/min Temperature: 25oc Chart Speed: 0.2 in/min -6-

UV Wavelength: 254 nm Injection: volume: 8·1-11 concentration: 10 pg/pl quantity: 80 pg Reference J.F. Laurence, 1976, "High Performance Liquid Chromatographic Analysis of Urea Herbicides in Food", J of the AOAC, 59, pp. 1066-1070. -7-

Table 1. Analytical Results of Technical Linuron Using HPLC.

Manufac- Compo- Ret en- turing Lot nents tion time Pk fo Company 4fo . 4fo (min) Area Total "A" T0110682 1 2.8 2 2.1

2 3.3 1.2 1.3 3 4.0 89.1 96.5 4 6.0 trace 5 0

"A" Tll02798 1 2.8 1.3 2.1 2 3.3 0.8 1.3 3 4.0 58 95.9 4 6.0 0.4 0.7 5 0

"A" Tll02584 1 2.8 4.5 5.0 2 3.3 2.3 2.5 3 4.0 84.0 92.5 4 6.0 t 5 0 "C" 1 2.8 1.9 2.9 2 3.3 0.8 1.2 3 4.0 62.0 95.3 4 6.0 0.2 0.3 5 7.0 0.2 0.3 8

Manufac- Compo- Ret en- turing Lot nents tion time Pk % Company #1 (min) Area Total

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b. Thin Layer Chromatograp0y (TLC) Woelm F 254/366 pre-coated silica gel plates were used for the TLC analysis. Solvent system consisted of 90% isooctane and 10% isopropanol by volume. One hundred micro grams (100]Jg) of technical Linu:ron was spotted in each plate, and developing time was 20 minutes. A typical developed TLC plate under short wave of a ultraviolet lamp (ultra-violet products, Inc) is depicted in Figure 2, the RF values of com ponents is summarized in Table 2.

-Solvent Front 7 --- 6 . 5 4 ~ 3 #1 2 #2 1 #3 0 - #4 Solvent Line

Figure 2. Thin Layer Chromatograms of "B" Technical Linuron Table 2. RF values of TLC Analysis of the "B" Technical Linuron Product. Component #1 #2 #3 #4 RF value . 43 .38 .15 .11 Estimated fo 0.5 0.5 1.0 98.0 RF value = Travel Distance of a component (em) I Travel Distance of solvent (em) -15-

c. Gas Chromatography - Mass Spectrometry (GC/MS) A Finnigan Model OWA-30B GC/MS/DS system was employed. GC column was 30 meter x 0.25 mm fused silica capillary of , durabond DB-5 (J&W Scientific Co). GLC and MS run conditions are reported in Tables 3 and 4. Analytical results are re ported in Figure 3. Although no distinct GC peaks were ob tained, RIC of all five samples were similar. The broad GC peak is due to thermal decomposition of Linuron in column. Lowering column temperature was attempted but components elution from the GC column was not satisfactory. Decomposition products were identified as (1) N,O-dimethylhydroxyurea

(C 2H70N); (2) methyl ester of 3,4-dichlorophenyl-carbamic acid (c H o Ncl ), and (3) N,N~-Bis-dichlorophenylurea (c H 0N cl ). 8 7 2 2 13 8 2 4 -16-

200 DEG = ZONE TEMP. 100 DEG = INITIAL TEMP. 250 DEG FINAL TEMP. 1 MIN INITIAL TIME 30.0 D/M- RAMP RATE 10 MIN = FINAL TIME 200 DEG = SEP. SET PT. 80 DEG = MANIF. SET PT. INJ MODE: CAP. 2 SEC = SPLIT/SWEEP VALVE TIME 40 SEC = FIL./MULT. OFF TIME FIL/MUL MODE: AUTO. SCAN FROM 30 AMU TO 650 AMU IN 4.0 Sec.

Table 3. GC Run Condition for Analysis of Technical Linuron. Table 4. Mass Spectrometer Run Condition (a) parameter settings 5-WAY SCAH A4 ON LINEAR OSPLV OU:CL CG:OH 07 DEC 82 09:41:11 EM UPPER LIMIT 2500 SMOOTHING FACTOR 1 9 EXTRACTOR 4.00 1 ELECTRON MULT SW OH 10 ELECTROMETR RHG 7.00 2 ELECT MULT VOLTS -1905.88 11 SCOPE SWEEP SW OFF 3 RESOLUTION HIGH 120.00 12 SCOPE SWP SPEED 1. 00 4 RESOLUTION LOW 127.00 13 ELECTROMTR ZERO -0.59 5 ION ENERGY 3.61 14 SCOPE 1ST MASS 389.02 6 FILAMENT SW OH 15 SCOPE MASS RHG 40.78 7 ION PROGRAM 1. 02 16 SCOPE SENSITVTY 0.05 8 LEHS VOLTAGE -72.16

i I. r ~ I I

309 10174 431 11016 I Table 4. Mass Spectrometer Run Conditions

(b) CF43 Report !AUTOMAT:IC TUNE RATIO REPORT .12/07/82 9:40:00 + 0:04 MASS :INTENSITY X OF 69 TARGET X 69 92~43. 1.00. 0e .100. 00 2 ..19 75647. 81. 74 30. 00- 60. ee 4l.4 2771.. 2. 99 1.. 40- 2. 00 :502 1.:543. l.. 66 0. 80- 2. 00

ISOTOPE RATIO REPORT MASSES ;. ISOTOPE TARGET 'Y. 69/ 70 1.. 23 0. 80- l.. 30 21.9/220 4. 35 3. ~0- ~. 20 41.4/41.~ 9. 48 7. 20-1.0. 80 502/~03 .10. l.6 8. l.0-l.2. l.0

:ALIBRATION REPORT: .18 • LOWEST PEAK rN REFERENCE TABLE FOUND 6.14 • HIGHEST PEAK IN REFERENCE TABLE FOUND 2.1 OF 2l. REFERENCE PEAKS WERE FOUND .L 7. OF PEAK WIDTH m RMS FIT ERROR Figure 3... . Reconstructed __Ion Chromatogram of Technical Linuron (a) RIC of "A" T0110682 RIC DATA: GRIFFIN11 SCANS 1 TO 203 12/07/82 16:04:00 SAMPLE: 10000NG 28 108. 184576.

50 100 150 200 SCAN Figure 3. Reconstructed Ion Chromatogram of technical Linuron

(b) RIC of "B" Product DATA: GRIFFIH21 SCAHS 1 TO 300 12/07/82 16:33:00 SAMPLE: 10000HG 29 100.0 134656

I 0 N I

77 94 Figure 3 . . Reconstructed Ion Chromatogram of Technical Linuron

190.9 29 85632.

I r-1 N I

RIC

91 , Figure 3. Recons·.tructed Ion Chromatogram of Technical Linuron

(d) RIC of "A" Tll02584 DATA: GRIFFIN41 SCANS 1 TO 300 12/07/82 17:23:00 SAMPLE: 10000~~G 29 100. 7731J

I N N I RIC I

_____ 1£i\~ Figu-re 3 .. Reconstructed Ion Chromatogram of Technical Linuron

(e) RIC of "C" Pro duet DATA: GRIFFIN51 SCANS 1 TO 300 12/07/82 17:51:00 SAMPLE: 10000NG

198. 27 143872. \

I ("') C'\1 I

50 100 150 200 250 300 SCAN ~--- -- ·- -··- -24-

d. Combination of TLC and GC/MS: TLC fractions developed from a series of identical con ditions were composited by scraping off from the TLC plates. Adsorped organic components were subsequently dissolved with methanol. Since very small quantities of organic compounds are present, we used glass capillary tubes to help in con centrating samples. Liquid samples collected in capillary tubes were then analyzed by injecting in GC port or in troducing to the solid probe vial of the mass spectrometer. TLC-MS (solid probe) Linuron & Impurities TLC-GC/MS Impurities only -25-

MASS LIST DATA: FRACT1 • 36 BASE M/E: 61 12/08/82 14:57:00 + 2:26 RIC: 9072. SAMPLE: SOLIDPROBE 30 0. 00 MINIMA MIN INTEN: 0. MAX INTEN: 1.902. 279 - 0 MAXIMA MASS ;. RA MASS 7. RA 30. 120 3. 1.5 1.60. 020 1.0. 20 31. 120 3. 58 1.60. 980 4. 78 32. 140 2. 21 1.62. 000 9. 62 33. 1.60 3. 52 1.62. 960 1.. 84 38. 080 1.. 89 1.67. 060 4. 63 39. 1.00 3. 00 1.86. 960 6. 83 41. 000 1.0. 20 187. 980 3. 79 42. 000 4. 05 1.89. 020 3. 84 43. 060 1.2. 93 248. 020 23. 71. 43. 980 4. 36 249. 080 1.. 74 44. 980 1.2. 78 250. 060 1.6. 46 46. 020 24. 50 251.. 1.40 1.. 58 . 55. 020 1.1.. 88 252:..160 3 . 58 56. 000 7. 1.0 279. 220 3. 79 57. 040 1.2. 67 58. 1.40 1.. 68 59. 020 4. 1.0 60. 020 20. 45 61.. 020 1.00. 00 62. 040 8. 41. 63. 000 6. 47 67. 020 3. 21. 69. 060 7. 1.0 70. 080 3. 52 71.. 020 6. 36 71. 940 2. 79 72. 960 6. 99 74. 000 8. 46 75. 000 5. 78 76. 060 1.. 74 81. 1.00 2. 37 83. 1.00 4. 1.5 84. 060 1.. 95 85. 280 1.. 68 87. 040 3. 89 88. 1.00 4. 00 90. 1.60 2. 47 94. 980 2. 21. 97. 1.00 4. 31. 1.08. 940 2. 00 1.23. 840 7. 52 1.25. 040 5. 57 1.25. 880 1.. 74 1.27. 1.20 1.. 68 1.33. 080 4. 63 1.34. 960 4. 84 1.45. 1.40 2. 94 1.47. 060 1.. 68 1.49. 060 1.0. 62 1.50. 020 1.. 74 1.59. 080 2. 63

Table 5. List of Mass of TLC Fraction #1 Table b. LIBRARY SEARCH of TLC Fraction {!=4 DATA: FRACT1 I 36 BASE M/E: 61 12/88/82 14:57:00 + 2:26 RIC: 8151. SAMPLE: SOL I DPROBE 1156 5AtA...E

C9.H18.02.H2.CL2 "WT1~~ B PK 61 RAN( 1 IH 17911 FIT 913

I ~ C.H3.02.H METHANE~ NITRO- I " WT11~. ~ 6~ IN 77 FIT 886 ·

.• al .a ' • • • I . • I • • I . ' BENZENE~ 1 ~ · 2-D I CHLOR0-4-METHVL-

se. 100 150 200 250 -27···

4. Physical and Chemical Properties

a. Physical properties: "B" Technical Linuron is light yellowish powder. Major physical properties of the product are listed below:

molecular weight 249~0

molecular formula

solubility in water (ppm)

melting point (°C) 93-94 -5 vapor pressure (rom Hg, 24°C) 1.5 X 10

b. Chemical properties: Significant chemical properties of Linuron are demonstrated in the following reactions.

(i) N-Demethylation and N-Demethoxylation

or H Cl ...... · ®0 -N-c-NH I Cl I o" ' CH3

(ii) Ring Hydroxylation or Substitution:

OCH H / 3 Cl-@ -N-c-N ~ II \ Cl I CH ° 3 -28-

(iii) Hydrolysis:

OCH3 HO OCH3 H / ,, I Cl - @o -N-c-N ·---4 Cl ··- .@ -NH2 + e-N I \l I II \ Cl o CH 3 Cl o CH 3

or OCH H I 3 Cl -@ -N-c-OH + H-N . 1 li ' Cl o CH 3 (iv) Thermal Decomposition:

H Cl-@ -N-c-OR ' n Cl 0

OCH 3 I + H-N ' CH 3