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The D and the L Isomers of 00P"-DDT Project Director: Dr. R. D. Kihrough

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The D and the L Isomers of 00P GEORGIA INSTITUTE OF TECHNOLOGY Engineering Experiment Station 0 PROJECT INITIATION Date: Project Title: The D and the L Isomers of 00 P"-DDT Project No.: B - 378 Project Director: Dr. R. D. Kihrough, Jr. Sponsor: Public Health Service . 1970 . Effective PCC9439r, XID 1969, ...... .. Estimated to run until: . • . Novembey Type Agreement: G111:1t. 1?0... 5P92:31-.03 ............... Amount;nt•. $ 11095* Reports: Terminal Progress Report due within six months after completion - ten copies. Contact Person: Dr. Otto A. Bessey, Chief Program, Dcv. and Eval. Branch Natl. Inst. of Env. 111th. Sci. National Institutes of Health U. S. Public Health Service Bethesda, Maryland 20014 *Excludes $129 to be transferred from unexpended balance of 13.61. Cost sharing requires additional *780; Cr.. panion Account =.:o. E-6o0-9144 Assigned to .... is41C1e4r .4-91.031 e4 PPierlce9 ..... Division COPIES TO: ❑ Project Director ❑ Photographic Laboratory ❑ Director ❑ Research Security Officer ❑ Associate Director ❑ Accounting ❑ Assistant Directoqs) a Purchasing ❑ Division Chiefs ❑ Report Section ❑ Branch Head ff.Library 0 General Office Services ❑ Rich Electronic Computer Center Engineering Design Services Itimp GEORGIA INSTITUTE OF TECHNOLOGY Engineering Experiment Station PROJECT TERMINATION Date 9/9/71 PROJECT TITLE: The D and the L Isomers of 0,P'-DDT PROJECT NO: PROJECT DIRECTOR: Dr. R. D. Eimbroughs Jr. SPONSOR: Public Health Service TERMINATION EFFECTIVE: 5/31/71 CHARGES SHOULD CLEAR ACCOUNTING BY: 7/31/71 Oblications Bemaininal Final Report - due 11/3/71 Dr. KintbrouGh) Final Patent Report - /WU CE111.) Nuclear & Diological Sciences Division COPIES TO: Project Director General Office Services Director Photographic Laboratory Associate Director Purchasing Assistant Directors Report Sectio Division Chief Library Branch Head Security Accounting Rich Electronic Computer Center Engineering Design Serviees 413:1- IC:UM tGl- X _it, INT C3 •X-• X WILT UV eCe 'X" M 43:E3E /41-1011 X. C)11S1--Se- EMINENT STATION 225 North Avenue. Northwest Atlanta, Georgia 3033.2 November 3, 1971 Division of Research Grants National Institutes of Health Bethesda, Maryland 20014 Gentlemen: Enclosed is the final report for project ES 00281. If further information is needed, please let me know. Sincerely, Raymond D. Kimbrough, Jr. Senior Research Chemist RDK:lsg Enclosure Final Report: The D and the L Isomers of o,p -DDT (Department of Health, Education, and Welfare, Public Health Service, Grant Number ES00281) Raymond D. Kimbrough, Jr. Nuclear and Biological Sciences Division Engineering Experiment Station Georgia Institute of Technology Atlanta, Georgia 30332 I. Reaction Pathways for the Synthesis of the Title Compounds 1. The simplest method of resolving the D,L mixture of ap t -DDT into the pure optical isomers would be by chromatography on a column of an opti- cally active material. The interaction of the D isomer and of the L isomer in the D,L mixture of ap t -DDT with cellulose, which has a D configuration, would be different and in many cases such a procedure has been used to separate the components of a D,L mixture. In the case of the D,L mixture of ap t -DDT, chromatography on cellulose, and on carboxymethylcellulose,did not produce any optical activity in the effluent. The reason for this is assumed to be that the very slight inter- action of the hydrophobic DDT and the hydrophillic cellulose was not adequate to produce any resolution. 2. The resolution of the D,L mixture of o,p'-DDT could be effected by synthesizing a molecule containing an amino group which could be used for. diastereomeric salt formation with an optically active acid such as d-10- camphorsulfonic acid. After the mixture is resolved, the amine could be diazotized and replaced by hydrogen or by a chlorine. Synthesizing such an amine or acetamido compound using a synthetic se- quence similar to the . one employed in the usual synthesis of DDT (chloral and 1 chlorobenzene in sulfuric acid or an ce-trichloromethly-p-chloro-benzyl alcohol and chlorobenzene in the presence of sulfuric acid or other Lewis acid) did not give the desired product. A suitable diamino compound was obtainable 1 2 from the reduction of the dinitration product of o,p'-DDT. ' The diazoti- zation of this diamine proceeded with dehydrohalogenation, equation 1, which would destroy any optical activity that had been obtained in the compound before diazotization. This dehydrohalogenation occurred with diazotization under all conditions which produced diazotization. diazotizatiodiazotization> CC1 3 -CHAr 2 -> CC1 2 = CAr 2 (1) ik asymmetric carbon 3. The resolution of the D,L mixture could be achieved by sulfonation of the aromatic rings, resolution of the diasteromeric sulfonate salt of an optically active base such as brucine, and subsequent removal of the sulfo- nate group. A disulfonic acid from both p,p'-DDT and o,p'-DDT was prepared, I and II, by reaction with sulfuric acid containing 10% sulfur trioxide at 0 70 C. The analytical and spectral, IR and nmr, data on these compounds were consistent with their structures. The positions for substitution of the aro- 1 matic rings would be the same in sulfonation as in the nitration. SO H 3 Cl 1 CC1 -CH- 0 H SO H 3 Cl 2 e The disulfonation of.I and II did not occur under the conditions usually used for this reaction, boiling 50% sulfuric acid. This reaction was attempted under a variety of conditions of higher temperature and both higher and lower concentration of acid. In every instance, dehydrohalogenation, equation 1, occurred before desulfonation. Hence, any optical activity would be lost on dXsulfonation. The sulfonates are new compounds. Their chemical and biological proper- ties are discussed below. 4. Phosphorus pentachloride is known to replace a hydroxyl group with a chlorine and a carbonyl group with two chlorine. The possibility of con- verting o-chlorophenyl-p-chlorophenyl—acetic acid, o,p'-DDA, which can be resolved (see below) to o,p'-DDT with phosphorus pentachloride (replacement of the hydroxyl of the carboxyl with a chlorine and the carbonyl of the car- boxyl with two chlorine) was attempted_. This conversion did not take place, but a new reaction of phosphorus pentachloride was obtained. These results are described in "Phosphorus Pentachloride for the Replacement of Benzylic Hydrogen with Chlorine." 3 [Reprinted from the Journal of Organic Chemistry, 34, 3655 (1969).] Copyright 1969 by the American Chemical Society and reprinted by permission of the copyright owner. Phosphorus Pentachloride for the Replacement butylbenzophenone and phosphorus pentachloride to of Benzylic Hydrogen with Chlorine' 185 ° , giving RAYMOND D. KIMBROUGH, JR. AND ROYCE N. BRAA1LETT 0 Nuclear and Biological Sciences Division, Engineering Experiment Station, Georgia Institute of Technology, Atlanta, Georgia 30332 Received April 10, 1969 Phosphorus pentachloride has been widely used to re- place the hydroxyl groups of alcohols and carboxylic acids to give alkyl chlorides and acyl chlorides, and to In the present work, it has been found that benzylic replace the carbonyl groups of aldehydes and ketones to hydrogen is replaced by chlorine when the material is give dichlorides. 2 heated with phosphorus pentachloride. The other prod- In specific cases, phosphorus pentachloride is known ucts of the reaction are presumably phosphorus tri- to replace carbon-bound hydrogen. Homophthalic chloride and hydrogen chloride. acid, I, with phosphorus pentachloride gives a series of The replacement of benzylic hydrogen may proceed by way of a free radical reaction pathway. The first step might be dissociation of the phosphorus pentachlo- CH,COOH ride to phosphorus trichloride and chlorine, a reaction known to occur at elevated temperature.' The chlorine COOH 0 would then react at the benzylic position in the familiar II manner.8 Cl, Toluene was converted to benzyl chloride by re- CCI,C0C1 fluxing with phosphorus pentachloride in almost quan- titative yield. With excess phosphorus pentachloride, Cl2 COC1 benzylidene chloride was obtained along with benzyl III IV chloride and unreacted phosphorus pentachloride. Thus the replacement of successive benzylic hydrogen products including II, III, and IV, where replacement seems to be increasingly difficult. of carbon-bound hydrogen with chlorine has occurred. 3 When diphenylinethane was heated with 1 mol of Phenyl malonate, V, and phosphorus pentachloride phosphorus pentachloride, benzhydryl chloride was give a mixture of products including VI and VII where formed. Excess phosphorus pentachloride gave di- replacement of carbon-bound hydrogen by chlorine has phenylmethylene chloride. Triphenylmethane was occurred.' converted to triphenylmethyl chloride in 93% yield by phosphorus pentachloride at 140-150°. 0 0 0 0 0 .0 (1) This research was supported by Grant No. ES 00251 from the National II II II II II II 6II5 Institutes of Health, U. S. Public Health Service. C61150CCH•C0C CICCC1,CC1 C8H5OCCCI,COC 6116 V VI VII (2) R. B. Wagner and If. D. Zook, "Synthetic Organic Chemistry," John Wiley & Sons, Inc., New York, N. Y., 1953, pp 91, 105, and 546. (3) W. Davies and H. G. Poole, J. Chem. Soc., 1616 (1928). (9) V.I. Shevchenko and A. V. Kirsanov, Zh. Obshch. Khim., 35, 713 (1965). (5) B. Fell, Angetv. Chem., 77, 506 (1965). Chlorination of hydrocarbons, specifically the chlo- (6) W. Theilacker and F. Boelsing, ibid., 71, 672 (1959). rination of heptane to give heptyl chloride, with phos- (7) A. F. Holleman and E. Wiberg, "Anorganische Chemie," 32nd ed,
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