Preparation of standards for aldicarb (Temik) metabolism study

propionaldehyde O-methylcarbamoyloxime] in cotton plants. (Bartley etal., 1969). In the study of aldicarb metabolism in plants it is necessary to cons...
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The Preparation of Standards for Aldicarb (Temik) Metabolism Study J o h n A. Durden, Jr., William J. Bartley, a n d John F. Stephen

The synthesis of 18 compounds of the general structure CH,XC(CH&R (where X is S, SO, or SOr and R is peracetic acid

CH3SH

+ BrC(CH&COOH

CH3SOC(CH3)nCOOH TiA

NaOH

___f

CH3SC(CH3)zCOOH

.1

6OCh

(excess)

T?A

CH,SC(CH&CONHOH < HzNOH CHaSC(CH3)ZCOCl + "2 CHsSC(CH,),CONH? THA

TAm

peracetic acid

peracetic acid

I

excess

I

excess

r-----l

1 equiv.

CH3SO?C(CH&CONHOH CH3SOC(CH&CONHOH TzHA

TIHA

456 J. AGR. FOOD CHEM., VOL. 18, NO. 3, 1970

1

1 equiv.

j. CH3SO?C(CH3),CONH? CH~SOC(CH~)ZCONH? T2Am

TIAm

Table I. Nmr Spectral Data of Aldicarb Metabolites and Related Standards CHa-X-C (CH3 ) 2-R Chemical Shifts (6) _______ -X-C(CH~)LCHa-CH_=NOH 1.35 and 1.43 2.41 so -CH=NOH ~

Compound TiO'* TLO"

TIAmh T2Amb TAP TiAl' TJAI'

2.78 2.70 3.12 2.09 2.53 2.93 1.96 2.51 2 96

DTI"

2.53

TIN* TiNb TAmb

-R (7.51) ( 7.32)

so so,

1.48 1 . 5 3 and 1 . 6 8 1.77 1.51 1 . 2 9 a n d 1.63 1.66 1.22 1 . 2 1 and 1 . 2 6 1.38

-C=N -C=N -CONH? (6.80) -CONE? -CONHa PCH2-0H - - (3.36), - (3.28) _____ -C&OH (3 . 6 6 ) , ( 4_ _._9_ _7 )

so

1 . 4 4 a n d 1 53

-CH=NOCNH? -

SO2

so

SOY

S

so SO? S

-

-

-Ck2-OH

-

(3.80). (3.50) __..__ 0 (7 82). (6 55) ..____

0 2.97 2.13 2.62 3.08 2.03 2.58 3.13

DT? TAc" TiAcC T Aci

THA' TIHA T HA " Aceto11i'-dr.

so2

-CH=NOCNH2 (7 87), (6.53) __.__ -COOH-( 1 1 5y) -COOH (1 1 09) PCOOH --CONHOH -CONHOH PCONHOH

1.62 1.50 1.51 1.61 1.47 1.49aiid1.50 1.64

S

so so2 S

so SO2

~

CDCIJ. 'D>O.

Again, due to competing sulfone formation, the sulfoxide alcohol (TIAl) was difficult to prepare in pure form. At room temperature with 1 equivalent of TAL and with 0.9 equivalent of peracetic acid, the product was a 70:30 mixture of sulfoxide and sulfone, respectively. At 0" C the product contained 3 to 5 % of sulfone. The use of sodium rnetaperiodate, a reagent reported t o give a high degree of selectivity in the sulfide to sulfoxide oxidation (Leonard and Johnson, 1962) gave results similar to those obtained with peracetic acid at 0 " C. TIAl was obtained in high purity by a reaction

However, the hydroxamic acid sulfoxide (TIHA) was obtained in a 1 :llmixture with its corresponding sulfone (T2HA), as indicated- by spectral and tlc data. The mixture was satisfactory for use as a tlc standard. The "desmethyl aldicarb" derivative, 2-methyl-2-(methylthi0)propionaldehyde 0-carbamoyloxime, DT, and the corresponding sulfoxide DTI, and sulfone DT?, were prepared according to Equation 2. No difficulty was encountered in the synthesis of DT and DT?, but DT1, like the preceding hydroxamic acid? TIHA, was obtained as a mixture with the corresponding sulfone. CHsSC(CHZ)?CH=NOH

COCln

CH3SC(CH,)?CH=NOCOCl

h"s + CH3SC(CH&CH=NOCONHz

TO

DT

I peracetic acid excess

1

CHySOK(CH3)2CH=NOCONHz

I equiv.

CH3SOC(CH3)2CH=NOCONH:!

DT2

DTi

The propanol derivatives (TAI, TIAl, and T2Al) were prepared according to Equation 3. ___~~_____

C H BSC(CHd2COCl

LAlHs

_____

C H 3SC(CH &CH?OH

TAI

I

1 peracetic acid

excess

(3 1

1 equiv.

-30' C

CHaSO&(CH&CHyOH

TzAI

CHaSOC(CH,),CHzOH

TlAl J. AGR. FOOD CHEM., VOL. 18, NO. 3, 1970 457

involving slightly less than one equivalent of peracetic acid at -4O”to -30°C. The following compounds described in this paper were identified as metabolites of aldicarb in cotton plants (Bartley et ul., 1970) (Table I); T1O, T20, TIN, T,Am. TIAI, TIAc. and T?Ac. In each case, sufficient quantities of these materials were synthesized for the required toxicological studies. The nmr spectra of these compounds are summarized in Ta ble I. ACKNOWLEDGMENT

The authors are indebted to G. E. O’Dell, E. B. Shamlin, and H. W. Stollings for invaluable technical assistance, Gratitude is also expressed to H. R. Joyce for infrared, C. B. Strow for nmr, and W. J. Lambdin and B. E. Wilkes for the high-resolution mass spectra.

458 3. AGR. FOOD CHEM., VOL. IS, NO. 3,

1970

LITERATURE

Bartley, W. J., Andrawes. N. R., Chancey. E. L.. Bagley, W. P., Spurr, H. W., J. AGR.FOODCHEM. 18, 446 ( 1970). Coppedge, J. R., Lindquist, D. A,. Bull, D. L.. Dorough H. W., J. AGR.FOODCHEM.15, 902 (1967). Hurd, C. D., in “Inorganic Synthesis,” H. S. Booth. Ed., Vol. I. p. 87-89, McGraw-Hill, New York, 1939. l i l i i . . Teclitrol. GotheizLarsson, E., Monies, L., Trans. Cl~ctlmer.~ burg, (Sweden). No. 47, 9 (1945); Chem. Abstr. 40, 2795 (1946). Leonard, N. J.. Johnson, C. R.; J . Org. Clzem. 27, 282 (1962). Metcalf, R. L., Fukuto. T. R., Collins. C.. Borck, K.. Burk, J., Reynolds, H. T., Osman. M. F.. J. AGR.FOODCHESI.14, 579 (1 966). Payne, L. K., Stansbury, H. A., Weiden, M. H. J.. J. AGR.FOOD CHEW14, 356 (1966). Smissman, E. E.. J . Amer. Chem. Soc. 76, 5805 (1954).

Receired for recieiv October 31, 1969. Accepted Fehrrini:v 18, 1970.