NOTES
Dec. 20, 1952 Anal. Calcd. for CsHW05N&Na: Found: N, 2.51; I, 45.2.
N, 2.55;
6297
I, 45.4.
occurring along with fluorine substitution. Some light may be thrown on the reason for this deamina1,2,5,6-Dibenz~nthranyl-9-ureidothyroxine .-Treatment tion by the observation of Schmelkes and Rubin7 of the sodium salt of the 1,2,5,6-dibenzanthrany1-9-ureidowho noted that if all the methanol used in washing thyroxine with ethanolic acetic acid as above gave a 73% yield of the free acid, m.p. 177-180' (dec.). Forrnol titra- the diazonium fluoborate was not completely retion of this material indicated negligible free amino group moved, some p-nitrotoluene was obtained in addinitrogen. tion to the expected 2-fluoro-4-nitrotoluene in Sodium Salt of 3,4-Benzpyreny1-5-ureidothyroxine(IIIc) . -One hundred milligrams (0.34 millimole) of 3,4-benz- preparing the latter by the Schiemann reaction. LI-ith the above facts in mind, i t seemed desirable pyreny1-5-i~ocyanate~~ and 0.272 g. (0.34 millimole) of the sodium salt of thyroxine in 10 mi. of anhydrous pyridine to see if more consistent yields in the deamination were treated as described above. The product, weight reaction could be obtained using the diazonium 0.155 g., yield 42%, dazkened at 160" and mclted with defluoborates. These salts can be obtained in good composition at 171-172 . yield and in excellent purity and, in addition, dnnl. Calcd. for C36H21OSK&Sa: h-, 2.50; I, 46.4. most of them are quite This paper reFound: S ,2.51; I, 46.2. ports the results obtained by decomposing several Acknowledgment.-The authors wish to thank the National Cancer Institute of Canada for grants different types of diazonium fluoborates with ethanol in the presence of zinc; investigation of the supporting this research. reaction of diazonium fluoborates with hypo(15) H . J. Creech, THIS JOURNAL, 63, 576 (1941). phosphorus acid and other deaminating reagents RAXTINC AND BEST DEPARTMEST O F blEDICAL RESEARCH is underway. The yields obtained (based on the YNIVERSITY O F TORONTO diazonium fluoborate used) are reported in Table TORONTO 6, CANADA 1; they are in most cases between 70-SOyO. The heterocyclic amines used gave quite low yields. Replacement of the Primary Aromatic Amino Interestingly enough, the yield of benzene from Group by Hydrogen Using Diazonium Fluoborates beiizenediazonium fluoborate was rather poor (46.5%) ; in this case, a 1% yjeld of biphenyl was B Y ARTHUR ROEA N D JACK R. GRAHAM1 produced-the only instance in which a coupling RECEIVED Aucusr 11, 1952 reaction occurred. Another curious fact about Many reagents have been used to replace the this reaction was that appreciable amounts of diprimary aromatic amino group by hydrogen; an ethyl acetal were formed; this compound was not excellent review of these methods has been given observed in any of the other deaminations. by Kornblum.'" No one of these methods is uniTABLE I versally applicable, and the yields vary conYield of product siderably with both the method and the amine from Diazonium diazonfluoborate used; all of these deaminations are carried out using ium borate, AuoDec. Yield, point, the diazotized amine. Usually the diazonium salt 1'1 orluct Am I l l e obtained 70 OC. 76 is not isolated ; occasionally, however, stabilized 91 lo4 l3etizenc 46.5" dry diazoniuin salts have been used. Thus Hodg- Auiline S8 104 82.2 Toluene son and Rfarsden2 stabilized diazotized amines with o-Toluidiiie 73.7 54 104 Toluene naphthalene-l,j-disulfonic acid or 2-naphthol-l- wz-Toluidiiie 90 106 84.8 Toluene sulfonic acid and decomposed the resulting dry p-Toluidine 91 166 70.4 Chlorobcnzeiie salt with ethanol in the presence of zinc or copper; o-Chloroaniline 82.6 Chlorobenzene they reported yields of the order of 90%. However, m-Chloroaniline 98 14s 89 153 x5,2 Chlorobenzene some workers have been unable to duplicate these p-Chloroaniline so 10.3 P!ietietole 71,(1 result^.^ Leslie and Turner4 obtained a 78% p-Phenetidine yield of 2-nitro-3'-bromobiphenyl from 4,4'-di- Ethyl p-amino97 95 benzoate Ethyl benzoate 09.2 amino-2-nitro-3'-bromobiphenyl by decomposing 88 141 Sitrobenzciic so, (1' thc bis-diazonium fluoborate salt in absolute ethanol p -l;itroaniliiic (30 142 S2.5 Biphenyl containing sulfuric acid. In this connection, i t is Benzidine 64.1 Saphthalccic of interest that Niemann, Benson and Meads P-Kaphthylaniiiie 93" 103 report the incidental preparation of about 7% of I n - Aminobenzo87 14s trifluoride Ueiizotrifluoridc 7 4 . 3 ethyl 3-fluoro-4-methoxybenzoate simultaneously with the formation of ethyl 3,5-difluoro-4-inethoxy-2-Bromo-4-mcth87 148 m-Broniotoluene 69 0 ylaniline benzoate in about 28% yield by the Schiemann 85-93 Quinoline 34 0 reaction6 from 2-methoxy-3-fluoro-5-carbethoxy-6-Aminoquinoline 95 93 Quinoline 31 :1 benzenediazonium fluoborate, some deamination 3-Aminoquinoline 91 (1) T h e work reported in this paper is taken from the master's thesis submitted b y Jack R. Graham t o t h e Graduate School of the UniverTity of Sorth Carolina, June, 1952. ( l a ) N. Rornhlurn, in "Organic Reactions,'' Vol. TI. Jvlin \Viley a a d Sons, inc.. Nrw \-
