FRANKKIPNISAND JOHN ORNFELT
1068
VOl. 74
[RESEARCH LABORATORIES, AMIUUCAN HOMEFOODS, INC. ]
Glyoxal Hemimercaptals BY FRANK KIPNIS’AND
JOHN
ORNFELT
A series of crystalline hemimercaptals was prepared by the interaction of glyoxals with mercaptans. be recrystallized from non-polar solvents and are stable over extended periods of time.
The products may
Hemimercaptals are rather unusual compounds it would seem that the hemimercaptals dissociate whose methods of preparation have not been on heating even in non-polar solvents, since the studied too extensively. A number have been solutions have a rather strong yellow coloration, prepared, derived from formaldehyde,* benzalde- indicative of the presence of the glyoxal, whereas hyde, methylglyoxal and phenylglyoxal with thio- in solid form, the compounds are colorless crystals glycolic acid derivatives and with cysteine, and which seem perfectly stable, showing no dissociahemimercaptols have been reported from a l l ~ x a n , ~tion or change in melting point after more than six polycyclic quinones6 and from a,P-diketones. months of storage. It will be noted that of the hemimercaptals from Phenylglyoxal,s p-ethoxyphenylglyoxaL0 thioglyoxals, only those have been prepared which phene-2-glyoxal1° and fury1-2-glyo~al~~ were precontain carboxylic functions. It was desirable pared by the oxidation of the corresponding methyl to prepare glyoxal hemimercaptals from alkyl, ketone with selenium dioxide. aryl and heterocyclic mercaptans containing no Most of the mercaptans were available from solubilizing groups. The results of this study are commercial sources. 2-Thenylmercaptan was preindicated in Table I. pared from 2-thenyl chloride via the isothiouronium TABLE
I
I~EMIMERCAPTALS R-CO-C
OH . -.
Ethyl n-Propyl i-Propyl n-Heptyl n-Dodecyl n-Hexadecyl n-Octadecyl Benzyl Phenyl Furfuryl fi-Cresyl
GH6 CaHr CeHr C HI CtHi CtHr CtHi CtHi GHI GHi CiHr
78-80 84 47-49 81 80-81 88 90.5-91 72-74 97-98 40 44-45
81.5 84 67 71 83.5 42.3 35.4 77.5 80 66 70
Recrystallizing solvent Ligroin Ligroin Ligroin Ligroin Hexane Heptane Hexane Ligroin Heptane Pentane Pentane
Thiophene-2-methyl n-Dodecyl Benzyl
p-CrH1-0-CtH4 ~-C;HFO-GH~ fi-CrHrO-CtH4
37-38 65-66 64-65
89 92 95
Hexane Hexane Hexane
CirHIaOiSr CzrHaaOzS CirHisOnS
58.42 69.43 67.52
5.23 9.53 6.00
n-Propyl n-Dodecyl %Hexyl
GHaO GHIO GHaO
Heptane Heptane Heptane
GHiZOaS CisHitOaS CirHiaOaS
53.98 66.22 59.47
n-Heptyl Methyl Ethyl n-Propyl Benzyl @-Naphthyl Thiophene-2-methyl n-Dodecyl Phenyl n-Octadecyl
GHaS QHaS GHaS
71 87 70 84 62 93 73
Heptane Hexane Hexane Hexane Hexane Hexane Hexane Hexane Hexane
89
Hexane
CIIH~OISI CrHlOBt C1HiiO:St CgHirOtSr CiaHiz0,St CiaHirOrSr CiiHiiOISi CIIHNOISI CirHioOISr CrrH4tOzSt
57.31 44.66 47.50 49.97 59.06 63.97 48.86 63.11 57,57 67.55
6.04 9.26 7.49 7.40 4.28 4.48 5.59 4.57 4.03 3.73 8.83 4.03 9.92
R’
a
R
GHIS CiHrS GHiS GHiS GHrS OHaS GHaS
M.p., OC.b
Yield.
% ’
105-106 98 99 105-106 91.5-85.5 94 76-77 91-93 58-69 69 78-79 98-99 54-55 80-81 55-56 91
74 84
Analyses by Oakwold Laboratories, Alexandria, Virginia.
It has been found possible to prepare crystalline hemimercaptals in good yields by mixing the glyoxal with the mercaptan and recrystallizing from the appropriate solvent. From visual evidence, ( 1 ) Oxford Products, Inc., Cleveland 3,Ohio. (2) T.G. Levi, Gass. chim. if&, 62, 775 (1932). (3) Fromm, Ann., 236, 135 (1889).
(4) M.P. Schubert, J. Biol. Chem., 111, 671 (1935). ( 5 ) E. L. d’ouville, F. J. Myers and R. Connor, THIS JOURNAL, 61, 2033 (1939). (6) A. SchonLcrg, 0. Schiitz, G. Arcnd and J. Peter, Bcr., 60, 2344 (1927). (7) (a) T. Reichstein and H. Staudinger, Swiss Patents 128,720, 130,605,130,606,130,607,130,608; (b) British Patent 260,960; (c) German Patent 489,613; (d) U. S. Patent 1,696,419.
b
Calculated Formula Carbon Hydrogen Ci@HiiOxS 61.19 6.17 6.71 CIIHI~OIS 62.83 62.83 6.71 CiiHiiOrS 8.32 CIKHISOB 67.63 9.58 CZ~HIIOIS 71.38 CriHuOrS 73.42 10.57 C ~ a H i r 0 B 74.23 10.54 5.46 CIOHIIOIS 69.74 68.83 4.95 CI4HlIO6 62.88 4.87 CiaHirOIS 69.74 5.46 CisHlrOrS
Analyses,o % Found Sulfur Carbon Hydrogen Sulfur
16.34 15.25 15.25 12.04 9.53 8.17 7.62 12.41
61.26 62.58 62.86 67.24 71.23 72.85 74.16 70.11 68.73 62.20 70.01
6.50 6.84 6.96 8.36 9.76 9.95 10.63 5.86 4.67 4.92 5.69
16.49 15.60 15.65 12.29 9.78 8.62 8.12 12.76
20.79 8.42
58.60 69.04 67.80
5.50 9.46 6.19
20.65 8.69
53.93 66.49 59.07
6.14 9.28 7.46
57.02 44.63 47.42 50.53 59.10 63.81 48.88 63.21 57.49 67.17
7.37 4.65 5.08 31.71 6.01 29.72 4.81 4.24 21.80 4.03 35.59 8.97 4.55 25.68 9.70 15.70
9.82 13.23
31.70 29.64 21.35 35.57 25.61 15.03
10.00 13.25
All melting points taken with Fisher-Johns apparatus.
salt.12 Furfuryl mercaptan has been prepared by several m e t h o d ~ , l ~but - ~ ~that of Reichstein” gave the most consistent results. (8) H. A. Riley and A. R. Gray, “Organic Syntheses,” Coll. Vol. 11, John Wiley and Sons, Inc., New York, N. Y.,1943, p. 509. (9) F. Kipnis, H. Soloway and J. Ornfelt, THISJOURNAL, 6B, 1231
(1947). (10) P.Kipnis and J. Ornfelt, ibid., 68,2734 (1946).
(11) F. Kipnis and J. Omfelt, iMd., 70,3948 (1948). (12) P.Kipnis and J. Omfelt, ibid., 71, 3571 (1949). (13) W.R. Kirner and G. H. Richter, ibid., 61,3134 (1929); W.R. Kirner, ibid., 60, 1958 (1928). (14) H. Staudinger and T. Reichstein, U.S.Patent 1,715,795. (15) J. Giral and A. Garcid Ferndndez, A n d e s ins!. inucsf.cicnl. Uni% Nucuo Leon, 1, 149 (1944).
Feb. 20, 1952
SPECTRA OF ARYLPHOSPHONIC AND DIARYLPHOSPHINIC ACIDS
Experimental Thiophene-2-gl ox& n-Heptylhemimercaptal.-Fourteen g i a m s (0.1 mole3 of thiophene-&glyoxal was mixed with 13.2 g. (0.1 mole) of n-heptyl mercaptan. A considerable amount of heat was’ generated, and on allowing the mixture to cool t o room temperature, the entire mass crystallized.
1069
The product was purified by recrystallization from heptane, giving colorless crystals melting at 76-77’ d. The other hemimercaptals were prepared in a similar manner. RECEIVED OCTOBER11,1961
MORRISPLAINS, N. J.
[CONTRIBUTION FROX VENEREAL DISEASEEXPERIIUENTAC LABORATORY, u. s. PUBLIC HEALTHSERVICE, SCHOOL OR PUBLIC HEALTH, UNIWRSTYOR NORTHCAROLINA]
The Ultraviolet Absorption Spectra of Arylphosphonic and Diarylphosphinic Acids BY H. H. JAFFSAND LEOND. FREEDMAN The ultraviolet absorption spectra of a number of arylphosphonic and diarylphosphinic acids, and of a few related compounds have been determined. These spectra indicate t h a t no resonance exists between a “pentavalent” phosphorus atom and a n aromatic nucleus attached t o it and that the P-0 bond in the phosphoryl group has no appreciable double bond character. Evidence is also presented which confirms the “keto” structure usually assigned t o benzenephosphonous acid.
In connection with a study of certain organic phosphorus compounds in this Laboratory, i t appeared desirable to investigate the effect of the phosphono (-POaHa) and phosphinico ( >P02H) groups on the ultraviolet absorption spectra of TABLE I Primary band mr
216
e m .
7,100
224 13,100 222 12,000 224 21,300
217 12,300 215 8,130 224 14,400
234 260 263 270 272 278 263 274 272
Secondary band
bu.
h x .
22,200 7,100 6,400 10,400 10,800 10,300 14,300 21,100 21,400
mr
e-.
254.5 180 263.5 524 263.0 383 258.0 239 264.5 616 263.5 477 265.0 1,200 264.0 882 265.5 2,420 261b l l , O O O b 264.0 206 270.5 798 271.0 649 264.0 292 273.5 1,738 273.0 1,390 265.0 1,000
272.5 1,250 (m-NO&H4)QHsPOzHu 263 7,570 (pNOzCsH4)GHpPOrH 272 11,500 (PNO&HI)C~HIPO~272 11,500 the spectrum of this compound has been previously determined by J. E. Purvis, J. C k m . SOC.,105, 1372 (1914). b It is uncertain whether these values should be assigned to the primary or secondary band. The purity of this compound was doubted at first when the spectrum was determined and the strong absorption band at 234 mp was observed. Therefore, the compound was recrystallized two more times from dilute alcohol; no change in the spectrum was noted. *Secondary primary band; . ,X 213, clap. 5,950. ‘Secondprimaryband: . ,A 216, b. 5,580. Second primary band: . ,X 218, 26,100. 9 Second primary bsnd: L, 210, c.r.19,600.
benzene and its derivatives. The present paper describes the results obtained with arylphosphonic acids, diarylphosphinic acids and a few related compounds.
rI
I
!
i !
j I
! !
!
240
260
280
mr. Fig. 1.-Absorption spectra: A, benzene; B, benzenephosphonic acid; C, benzenephosphonous acid; D, diphenylphosphiiic acid; E, triphenplphosphine oxide.
Experimental All compounds studied were prepared in this Laboratory. The synthoah of the Prylphosphoafa and the symmetrical
