1,3-dithiole derivatives from acetylenic compounds substituted with at least one electron-withdrawing group and carbon disulfide
United States Patent 91 Hartzler Apr. 8, 1975 1,3-DITHIOLE DERIVATIVES FROM ACETYLENIC COMPOUNDS SUBSTITUTED WITH AT LEAST ONE ELECTRON-WITHDRAWING GROUP AND CARBON DISULFIDE [75] lnventor: Harris Dale Hartzler, Wilmington.  
 Del.  
 [73] Assignee: E. I. du Pont de Nemours and Company, Wilmington, Del.  
 [22] Filed: June 6, 1973 [2]] Appl. No.: 367,879  
 Related U.S. Application Data [62] Division of Ser. No. 47,lll, .lune I7. 1970,  
 abandoned.  
 [52] U.S. Cl 260/327 M; 260/240 R; 106/3 [5 1] Int. Cl C07d 7l/00 [58] Field of Search 260/327 M. 240  
 [56] References Cited UNITED STATES PATENTS 3.758.503 9/l973 Hartzler 260/327 3.781.28l l2/l973 Hartzler 260/240 OTHER PUBLICATIONS Krespan, et al.. J. Org. Chem. 33: l850-l854 (l968).  
 Primary E.\&#39;aminer-Henry R. .liles Assistant Examiner-C. M. S. .Iaisle [57] ABSTRACT Acetylenic compounds R&#39;C CR in which at least one of the R and R substituents is an electronwithdrawing group react with carbon disulfide to give dithiole compounds of three different formulas, their ratio depending on the reaction parameters. In the presence of a coreactant HX, a dithiole substituted with the X group in the 2-position is formed. In the presence of a carboxylic acid or of an ethylenic compound, acetylenic compounds RC CR react with carbon disulfide to form other 2-substituted dithioles. The novel compounds of this invention are useful in removing tarnish from silverware.  
 9 Claims, No Drawings 1,3-DITHIOLE DERIVATIVES FROM In the presence of a coreactant I-IX, the substituted ACETYLENIC COMPOUNDS SUBSTITUTED WITH 1,3-dithiole of formula (4) is formed AT LEAST ONE ELECTRON-WITHDRAWING GROUP AND CARBON DISULFIDE R -C-S /H RELATED APPLICATION 5 I This application is a division of US. Ser. No, 47,1 1 l 2 filed June 17, 1970, now abandoned. R x  
 I BACKGROUND OF THE INVENTION In the above formulas X can be one of the following 1. Field of the Invention groups: This invention relates to novel 1,3-dithiole derivaa, lower alkoxyl; tives, which are obtained from carbon disulfide and b. 0- or p-hydroxyphenyl, optionally substituted with certain acetylemc compounds, optionally in the presup t t groups, hi h i di id ll can b h l ence of selected coreactants. gen, lower alkyl, lower alkoxyl, alkoxycarbonyl of 2. Prlor Art up to 12 carbon atoms, benzoyl, hydroxyl, the nitro Krespan and England, J. Org. Chem. Soc., 33, 1852 group or the c ano group; (1968) reported the formation of the compound c, C()(CH=CH R h i n i 0 or 1 d R i aryl of up to twelve carbons or alkaryl of up to s C CF twelve carbons, both optionally substituted with halogen, lower alkoxyl, lower alkoxycarbonyl, ben- H zoyl, the nitro group, or the cyano group;  
 CF C S (3P 3P CF. c s s c CF by a reaction of hexafluoro-Z-butyne with sulfur and carbon disulfide at 200C. I 1  
 Acetylene itself is known to react with carbon&#39;disulfide, giving thiophene. c  
  SUMMARY OF THE INVENTION It has now been discovered, according to the present invention, that acetylenic compounds of the formula RC 5 CR where R, R R and n are as defined above; and  
  e. in which R is an electron-withdrawing group, such as cari boxyl, alkoxycarbonyl of up to 12 carbon atoms, i aryloxycarbonyl of up to 13 carbon atoms (including the carbonyl carbon), lower perfluoroalkyl, arylcarbonyl of up to 13 carbon atoms (including the carbonyl carbon), or the cyano group; and R is either the same as R or hydrogen, a C -C alkyl,  
  aryl of up to 12 carbon atoms, or alkaryl of up to 45 where 12 carbon atoms R is hydrogen, lower alkyl, or aryl of up to twelve react with carbon disulfide to give products having carbons; the following formulas (l), (2), and (3), their ratio de- R is hydrogen, lower alkyl, lower alkanoyl, or aryl of pending on the reaction conditions. up to twelve carbons;  
  -C-COR6,  
 R is hydrogen, lower alkyl, aryl of up to twelve carbons, or alkaryl of up to twelve carbons; but  
 R and R taken together can be alkylene of from two to twelve carbons.  
  Substituted acetylenes of the formula RC=CR wherein R has the above-defined meaning, react with carbon disulfide in the presence of a carboxylic acid I-IZ, in which Z is an aroyloxy group or an alkanoyloxy group of up to 13 carbon atoms, or in the presence of ethylenic compounds having the formula CH =CHR in which R&#34; is hydrogen, lower alkyl, an alkanoyloxy group of up to 13 carbon atoms, or phenyl. The products obtained in the above reactions can be represented by the following formula R c s\ R-C-S R being defined above. The products of this invention are useful for removal of tarnish from silverware.  
 DETAILED DESCRIPTION OF THE INVENTION While all the products of the present invention have one or more 1,3-dithiole rings in their molecules, their structures vary with either the starting materials or the reaction parameters. Among the simpler reaction products are those shown by formulas (4) and (5), above.  
  Compounds having the general formula (4) are formed in a reaction of an acetylenic compound RC=CR with carbon disulfide and a coreactant HX; R, R and X having been defined above. Depending onthe nature of X, the coreactant HX can be a lower alcohol, a phenol with at least one unsubstituted ortho or para position, an aldehyde or ketone containing at least one a-hydrogen, benzaldehyde or a derivative thereof, or cinnamaldehyde or a derivative thereof. The term lower alcohol means an aliphtatic alochol having up to five carbon atoms.  
  Representative I-IX coreact&#39;ants include methyl alcohol, ethyl alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol (all isomers) amyl alcohol (all isomers),  
 2-chlorophenol, 4-chlorophenol, 2,6-dichlorophenol, 4-bromophenol, m-cresol, o-cresol, 2,3- dimethylphenol, 3,5-dimethylphenol, 2,4-  
 dimethylphenol, p-ethylphenol, p-methoxyphenol, oethoxyphenol, p-propoxyphenol, methyl salicylate, ethyl salicylate, methyl p-hydroxybenzoate, butyl mhydroxybenzoate, resorcinol, hydroquinone, catechol, p-nitrophenol, m-nitrophenol, o-nitrophenol, salicylonitrile, p-hydroxybenzonitrile, 2-hexylphenol, 2-bromophenol, 3-fluorophenol, 4-iodophenol, 4- chloro-3-fluorophenol, 5-butyl-2-chlorophenol, 3,5- xylenol, 2-isopropyl5-methylphenol, 2,6- dichlorophenol, m-isopropoxyphenol, and butyl salicylate.  
  HX can further be, for example, acetaldehyde, 2- methylpropanal, propionaldehyde, valeraldehyde, heptanal, dodecanal, tridecanal, acetone, methyl ethyl ketone, diethyl ketone, butyl ethyl ketone, dihexyl ketone, acetophenone, ethyl phenyl ketone, diphenyl ketone, propyl naphthyl ketone, butyl anthryl ketone, cyclopentanecarboxaldehyde, cyclopentanone, cyclohexanone, cycloheptanone, benzophenone, phenyl naphthyl ketone, 2-ethyl-4-methylpentanal, phenylacetaldehyde, l-( 2-naphthyl)-2-butanone, a,a-diphenylacetophenone, 2-methyl-3-hexanone, 2 ,2-dimethyl-3-heptanone, S-pentadecanone, 5-methyl-2,4-hexanedione, 7-methyl-2,4-nonanedione, 3-methyl-2,4-pentanedione, 2 ,6-dimethyl-3 ,5-  
 heptanedione, 5,5-dimethyl-2,4-hexanedione, 2- acetonaphthone, 3-phenylacetophenone, 4- methylpropiophenone, 3-ethylacetophenone, 2 ,4,6-  
 trimethylacetophenone, 4-t-pentylacetophenone, cyclobutanone, p-hydroxybenzophenone, 3-methylcyclopentanone, cyclododecanone, 3-isopropylcyclohexanone, and 3-ethyl-S-methylcyclohexanone.  
  HX can also be benzaldehyde, cinnamaldehyde, naphthaldehyde, anthraldehyde, naphthylvinylaldehyde, and anthrylvinylaldehyde; as well as their substituted derivatives in which the substituents can be, for example, chlorine, bromine, iodine, fluorine, methoxyl, ethoxyl, propoxyl, isopropoxyl, pentoxyl, isopentoxyl, methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, pentoxycarbonyl, benzoyl, the nitro group, or the cyano group.  
  Such substituted aldehydes include, for example, the following compounds: 3,S-dimethylbenzaldehyde, 2- phenylbenzaldehyde, p-(sec-butyl)benzaldehyde, 2,4,6-triethylbenzaldehyde, p-isopropylcinnamaldehyde, o-methylcinnamaldehyde, pphenylcinnamaldehyde, Z-naphthaleneacrolein, 4- isopropyl l ,6-dimethylnaphthaldehyde, S-nitrol naphthaldehyde, p-ethoxycinnamaldehyde, mchlorobenzaldehyde, o-isopentyloxybenzaldehyde, mcyanobenzaldehyde, p-methoxycarbonylbenzaldehyde, o-nitrobenzaldehyde, and p-benzoylbenzaldehyde.  
  R can be a lower alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, and isoamyl; an aryl, such as phenyl, a-naphthyl, ,B-naphthyl, or anthryl; or alkaryl, such as o-tolyl, mtolyl, p-tolyl, xylyl, duryl, ethylphenyl, a methylnaphthyl, an ethylnaphthyl, or propylphenyl.  
  R can, in addition, be the same as R, which is, among others, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, naphthoxycarbonyl, anthryloxycarbonyl, trifluoromethyl, pentafluoroethyl, heptafluoropropyl, benzoyl, toluoyl, naphthoyl, or anthranoyl. As stated earlier, R and R can also be carboxyl or the cyano group.  
  Acetylenic compounds which are suitable as starting materials for the practice of this invention include, among others, the following: hexafluoro-Z-butyne, dimethyl acetylenedicarboxylate, diethyl acetylenedicarboxylate, methyl propiolate, ethyl propiolate, propiolic acid (2-propynoic acid), tetrolic acid (2-butynoic acid), 2-octynoic acid, phenylpropiolic acid, mtolylpropiolic acid, l-naphthylpropiolic acid, 4- biphenylylpropiolic acid, ethyl tetrolate, butyl phenylpropiolate, phenyl propiolate, 3,3,3-trifluoropropyne, 3 ,3,4,4,4-pentafluorol -butyne, l, l l -trifluoro-2- butyne, l l l -trifluorophenylpropyne, 3-butyn-2-one, l-hexyn-3-one, 4-octyn-3-one, 3-undecyn-2-one, 4-phenyl- 3-butyn-2-one, l-phenyl-Z-hexyn- 1 -one,  
  heptyne,&#39;3-hexyne-2,5-dione, -decyne-4,7-dione, 1,4-  
 butyne-2-butyne1,4-dione, l,4-bis( 3,5-xylyl)-2- butyne-l ,4-dione, l ,4-di-p-tolyl-2-butynedione, and acetylenedicarbonitrile (dicyanoacetylene or butynedinitrile).  
 Preparation of compounds of Formula (4) does notrequire exact stoichiometric amounts of the starting materials. In practice, excess of both carbon disulfide and the coreactant is preferred. Although a tenfold, or  
 even higher, excess of either one of these two starting materials can be used, it is not practical to exceed the CS RC IE CR or HX R C E CR molar ratio of 2:1 to 3:1.  
  The reaction is carried out at a temperature of about 45150C. The rate of reaction decreases with decreasing temperatures, and the reaction is quite slow at aboutt 30C. Temperatures above 150C. can be used,  
 but it is not advisable to exceed about 200C. because of thermal instability of the products.  
 This reaction can be run at either normal pressure or at superatmospheric or subatmospheric pressure. Be-  
 cause of the high volatility of carbon disulfide and of the volatility of certain acetylenic compounds and of the I-IX coreactants, it is convenient to conduct this process at autogeneous pressure in a closed system. However, the process is not limited to batch operations and can, at sufficiently high pressures and temperatures, be adapted to continuous operations. Under autogeneous pressures, within the preferred temperature range, the reaction time varies from several hours to several days.  
  No solvent need be added to the reaction mixture, but excess carbon disulfide or HX reactant serves at the same time as the reaction solvent. Unsubstituted aliphatic esters, ethers or nitriles also can be used as solvents.  
  Compounds of Formula (5) can be prepared by contacting an acetylenic compound, RC E CR, and carbon disulfide with a lower alkanoic acid, an arenecarboxylic acid, or alkarencarboxylic acid of up to 13 carbon atoms. A lower alkanoic acid for the purpose of this invention is an alkanoic acid having no more than six carbon atoms. Typical carboxylic acids which are useful in this process include: formic, acetic, propionic, butyric, isobutyric, pentanoic, hexanoic, benzoic, land 2-naphthoic, anthranoic, 0-, m-, and p-toluic, dimethylbenzoic, ethylbenzoic, 8-methyl-l-naphthoic, 2,4,6-triethylbenzoic, 4-pentylbenzoic, trimethylacetic, a-ethylbutyric, and ethylnaphthoic acids.  
 &#39; The reaction product will have the formula (5),  
 above, in which Y is hydrogen, and Z is the alkanoyloxy or aroyloxy group derived from the starting acid.  
  Reaction of an acetylenic compound R C E CR with carbon disulfide and an ethylenic compound CI-I =CHR leads to the product having the formula (5), in which Y and Z taken together form the group /cHP. \L,  
 The radical R can be, among others, a lower alkyl,  
 such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl,  
 sec-butyl, tert-butyl, or pentyl (all isomers). It also can be a lower alkanoyloxy group, such as formoyloxy, acetoxy, propionoxy, butanoyloxy, pentanoyloxy, and various isomers of the last two named radicals. R can also be hydrogen or phenyl. Representative ethylenic compounds include: vinyl butyl ether, vinyl 2-ethylhexyl ether, vinyl l-isopropyl-2-methylpropyl ether, vinyl acetate, vinyl isobutrate, vinyl heptanoate, propylene, isobutylene, and l-heptene.  
  Theprocess conditions are similar to those discussed above in connection with compounds of formula (4), and the effects of process variables are comparable.  
  Products of formulas (1), (2), and (3) are made by contacting an acetylenic compound RC 5 CR with carbon disulfide. By varying the conditions, any one of these types can be formed predominantly or exclusively.  
  The formation of Type (1) can be favored by adding a lower alkanoic acid or a lower haloalkanoic acid to the system as a promoter or catalyst. Such an acid will have a pK (in an aqueous solution, at 25C.) of less than about five. The lower the pK,,, i.e., the stronger the acid, the higher will be the yield of a product of Formula (l). Haloalkanoic includes monohaloalkanoic and polyhaloalkanoic, including perhaloalkanoic. The  
 preferred halogen substituents, for economic reasons, are fluorine and chlorine. Suitable acids, together with their pK s, include formic acid (3.75), acetic acid (4.76), isovaleric acid (4,77), iodoacetic acid (3.18), a-bromopropionic acid (2.97), difluoroacetic acid (1.24) and trichloroacetic acid (0.92). The pK values of many such acids (or K, values, from which pK can easily be calculated) are given, for example, in Handbook of Organic Structural Analysis, Ed. Yukawa (Benjamin, 1965), pages 614 ff. Also, see the discussion following Example 23, below.  
  The acid concentration usually is maintained between about 0.1 mole and 1 mole per mole of the acetylenic compound. The catalytic effect of the acid is still perceptible at molar ratios as low as about 0.01:1. Although any large amount of the acid can be used, there is no advantage to exceed the molar ratio of about 3:1.  
  ln the absence of a carboxylic acid catalyst, compounds of Formulas (2) and (3) are the principal products. Carbon disulfide is usually present in a larger than equimolar amount with the acetylenic compound. A small excess of carbon disulfide favors the formation of a product of Formula (3), while a larger excess (e.g., 5-10 moles of CS for each mole of the acetylenic compound) favors the formation of a product of Formula (2). The effects of temperature, pressure, and reaction time are comparable with those discussed above in connection with compounds having the formula (4).  
  This invention is now illustrated by the following representative examples of certain preferred embodiments thereof.  
  All the experiments described in the examples were carried out in sealed glass or stainless-steel tubes. After the stated period of heating, the tubes were cooled before being opened. All temperatures are in C. In pressure measurements, the term torr&#34; is equivalent to millimeters of mercury. In nuclear magnetic measurements (nmr) data, the numbers in brackets refer to relative intensities. Infrared absorption spectra of liquids were taken on the pure materials; spectra of solids were determined on potassium bromide discs. In the infrared data, the absorption frequencies are in cm.&#39;, and terms (s), (m) and (w) correspond to strong, medium and weak absorption. In the, ultraviolet absorption data,  
 nm stands for nanometers and sh means a shoulder.  
 4,5-Bis( tritluoromethyl)-2-methoxy-1 ,3-dithio1e EXAMPLE 1 CF -S A mixture of ml. of carbon disulfide, 15 ml. of methanol, and 16 g. of hexafluoro-Z-butyne was heated at 100 for 2 days. Distillation of the product gave 5.6 g. (21%) of 4,5-bis(trifluorornethyl)-2-methoxy-l,3- dithiole which boiled at 80 at 24 torr, n 1.4255.  
 Anal. Calcd. for C H F OS C, 26.27; H, 1.49; S,  
 23.73; F, 42.19 Found: C, 26.64; H, 1,46; S, 23.78;  
  F, 42.26 F nmr: Singlet at +3138 c.p.s. from trihclorofluoromethane.  
 H nmr: Singlets at 83.09 [3] and 86.43 [1].  
 IR: Double bond C=C absorption at 1595 emf.  
 UV: ln isooctane, Ash 287 (63210), 269 (63910) and 212 nm (c3670).  
 Mass spectrum:  
 1161 111. 22.113.111 [ism 270 1320 Parent 239 224,900 r-ocna 40 201 385 P-CFa CF3 19 4 692 CF3C=C T S 157 1 191 chow-s 1 13 1119 cF c| or so 125 1029 cF ccs EXAMPLE 2 cr c-s a I ll C CF30 -S OCHQCH:  
  A mixture of 15 ml. of ethanol, 15 ml. of carbon disulfide, and 16 g. of hexafluoro-2-butyne was heated at 100 for 3 days. The reaction mixture was distilled. 4,5- Bis(trifluoromethyl)-2-ethoxy-l,3-dithiole was collected at 7073 and 10 torr, 17.1 g., n 1.4264.  
 Anal. Calcd. for C H F OS C, 29.57; H, 2.12; S,  
 22.56; F, 40.11 Found: C, 19.51; H, 2.08; S, 22.54;  
 H nmr: Methine CH) [l] singlet at 86.42, methylene (CH quartet [2] centered at 83.38, and methyl triplet [3] centered at 81.03.  
 1R: Double bond at 1590 cm.&#34; and strong, broad C-F absorption.  
 EXAMPLE 3 4-Carbomethoxy-2-methoxy-1,3-dithiole (Formula 4; R=COOCH R H; X=OCH H C-S a H c CH OOCC-S OCH;  
  A mixture of 9 g. of methyl propiolate, 15 ml. of carbon disulfide, and 15 ml. of methanol was heated at for 4 days. Distillation gave 2.7 g. of 4- carbomethoxy-Z-methoxy-l,3-dithiole, b.p. 99 at 0.9 torr, n 1.5696.  
 Anal. Calcd. for C H O S C, 37.48; H, 4.20; S, 33.36  
 Found: C, 37.65; H, 4.20; S, 33.28  
 H nmr: Methine resonance at 87.32 [1] and 6.89 [l] and methoxyl resonance at 83.67 [3] and 3.07 [3].  
 IR: 3000(m), 1710 (s), 1550 (s), 1440 (s), 1340 (w), 1280 (s), 1250 (s), 1210 (m), 1190 (m), 1050 (s), 950 (m), 900 (s), 850 (m), 830 (m), 770 (s), 750 (s), 730 (s).  
 UV: 1n ethanol, A304 (66600) and sh 230 nm (c4050).  
 EXAMPLE 4 4-Carbethoxy-2-methoxy-1,3-dithiole (Formula 4; R=COOC H R =H; X=OCH CligCHgOOC IT &#39;8 H HC&#39;S OCH A mixture of 20 g. of ethyl propiolate, 20 ml. of carbon disulfide, and 20 ml. of methanol was heated at 100 for 4 days. Unchanged starting materials were removed under reduced pressure. The residue was distilled through a micro column to give 3.0 g. of 4- carbethoxy-2-methoxy-l ,3-dithiole, b.p. 9295 at 0.5 torr, n 1.5656.  
 Anal. Calcd. for C H O S C, 40.75; H, 4,89; S, 31.09  
 Found: C, 40.86; H, 5.05; S, 31.03  
 H nmr: Methyl triplet centered at 81.23 [3], methoxyl singled at 83.12 [3], methylene quartet centered at 84.18 [2], and methine singlets at 86.98 [1] and 7.40 [1].  
 IR: 3000 (m), 1700 (s), 1550 (s), 1450 (m), 1390 (w), 1360 (m), 1280 (s), 1250 (s), 1200 (m), 1180 (m),  
  9 10 1090 (m), 1050 (s), l000(m),920 (m),900(s),880 IR: 3330 (m), 1605 (s), 1515 (m), 1500 (m), 1460 840 (m), 1330 (m), 1270 (s), 1180 (s), 1140 (s), 1090 UV: In ethanol, A 304 (56080) and sh 230 nm (68 (m), 1040 (m), 920  
 4260) UV: In isooctane, A 325 (62590) and 282 nm (E3980).  
 EXAMPLE 5 5 4,5-Bis(Carbomethoxy)-2-methoxy-1,3-dithiole EXAMPLE 7 (Formula 4; R =R =COOCH X=OCH Dimethyl CH OOCC -S H 2-(2,5-dichloro-4-hydroxyphenyl)-1,3-dithiole14,5-  
  C dicarboyxlate (Formula 4; R=R =COOCH CH 0000 -S 001-1 X=2,5-dichloro-4-hydroxyphenyl) A mixture of ml. of carbon disulfide, 15 ml. of CH 00c s methanol, and 14.2 g. of dimethyl acetylenedicarboxy- 3 late was heated at 100 for 3 days. The addition of ether 15 c1 to the contents of the tube precipitated 6.3 g. (25%) of crude 4,5-bis(carbomethoxy)-2-methoxy-1,3-dithiole, CH3 003 s m.p. 3944. Recrystallization from methanol raised the melting point to 60.5-61.5.  
  C1 Anal. Calcd. for C H O S C, 38.38; H, 4.03; S, 25.62  
  Found: C, 38.42; H, 4.18; S, 25.53 A mixture of 36 g. of dimethyl acetylenedicarboxy- H1 nmr! M y singlet at 53-30 h l y late, 50 g. of 2,5-dichlorophenol, and 100 ml. of carbon bonyl smglet at 83-82 and methme Smglet at disulfide was heated at 130 for 8 hours. Filtration of the reaction roduct ave 24 3 of crude dimeth l 2- UV: In ethanol, A 314 (65120), 238 (63780), and 218 l ydroiyphenylf1 3 dithiole 4 5- y nm (3190)&#39; dicarboxylate which melted at l34-l36. Recrystalliwhen the reaction was run at 1300 for 8 hours a 60 zation from ethanol raised the melting point to percent yield was obtained. 1779-1780 Anal. Calcd. for C l-l Cl O S C, 40.92; H, 2.65; CI,  
  EXAMPLE 6 18.60; s, 16.82 P6111111; c, 41.28; H, 2.88; (:1, 18.39; 4,5-Bis(trifluoromethyl)-2-(4-hydroxyphenyl)-1,3- S, 16.89  
 dithiole (Formula R1=R2=CF$ y yP y l-l nmr (in hexadeuterioacetone): Methyl [6] singlet at 35 83.23, dithiole hydrogen singlet [1] at 85.80, and arfi S c H omatic hydrogen singlets at 6.60 [1] and 87.24 [1].  
 CF30 There was a broad resonance at 82.55 [1] for the hydroxyl hydrogen. This moved to lower field upon ad- 40 dition of D 0. The absence of coupling between the A mixture of 20 of P 20 of carbon disul&#39; two aromatic hydrogens indicates that they are para fide, and 16 g. of hexafluoro-Z-butyne was heated at 100 for 3 days. The reaction mixture was distilled IR, 3300 m),2970 w 1740 s 1700 s 1600 m through a short st1ll head to g1ve 17.7 g. of 4,5- 1580 148-0 5) 1 0: 8 25; B1s(tr1fluoromethyl)-2-(4-hydroxyphenyl)-1,3- 0 1220 (S) 00 )l080 1025 dithiole, b.p. 125-136 at 0.5 IOU, 111. 1. 51-56. Re- 1 1 m 1 s 1 m 1 970 (m), 950 (w), 910 (w), 885 (w), 875 (w), 860 l f h d th l[ t t zrsyitggllgation rom exane ra1se e me mg pom o 830 785 (m), 770 (w), 760 (m), 750 (w),  
  730 (w), 700 111 690 111 A1181. Calcd. fOl c H FOS. c, 39.75, H, 1.82, s,  
 1930 F 34.31 g i 23998 H 188 S uv. 1116111111161, 1,...350 (e4080)and 286 1111146400 to each other.  
  5 EXAMPLE 8 F nmr: Smglet at +3163 c.p.s. from trichloroflu- 2 BenZoy1 4,5 bis(trifluoromethyl) 13 dithio1e and oromethane. 2-b ]-4 4&#39;, A g e at 66-22 l and an aromatic multi- 5,5-tetrakis(trifluoromethyl)-2,2-di-(1,3-dithiole) I plet [5] which included the hydroxyl hydrogen. (Formula 4; R =R =CF X=C H CO or COC H s-0c1=&#39; -C s-ccF CFS &#34;C CF C-S H! cs c 11,,cHoll c11-coc 11 CF -C CF C -S (m c-s l s-ccrz,  
 &#39; ll ll cr c-s S-CCF A mixture of 20 ml. of carbon disulfide, 15 g. of benzaldehyde, and 16.5 g. of hexafluoro-Z-butyne was heated at 100 for 6 days. The volatiles were removed under reduced pressure, leaving an oily residue. Some solid was obtained by adding hexane. Filtration gave 1.8 g. of pale yellow solid, mp. 82-86. Recrystallization of part of this solid from hexane gave 2-benzoyl- 4,5 -bis(trif1uoromethyl)-1 ,3-dithiole, m.p. 8788.  
 Anal. Calcd. for C H F OS C, 41.86; H, 1.78; S, 18.62; F, 33.11 Found: C, 41.28; H, 1.75; S, 19.17; F, 34.39  
  F nmr showed one peak at +3173 c.p.s. from trichlorofluoromethane. H 1 nmr showed an aromatic multiplet and a singlet [1] at 86.19.  
 IR: 1690 (s), 1610 (s), 1590 (m), 1450 (m), 1270 (s), 1160 (s), 1080 (m), 1000 (m), 990 (m), 925 (m), 850 (m), 820 (m), 780 (m), 735 (m), 720 (m), 700 (m), 685 (m), 660 (m).  
 UV: In isooctane, A sh 357 (e743), sh 310 (2000), 249  
  Part of the filtrate residue from above was chromatographed on a commercial analytical adsorbent (Florisil). Elution with hexane yielded crystalline 2-benzoyl- 4,4, 5,5 &#39;-tetrakis(trifluoromethyl)-2,2&#39;-di-( 1,3- dithiole), m.p. 4345.  
 Anal. Calcd. for C H F OS C, 35.05; H, 1.04; S, 22.02; F, 39.14; MW, 582.50 Found: C, 35.20; H, 1.17; S, 22.01; F, 40.32; MW, (mass spec, m/e 582) F nmr showed two peaks of equal intensity at +3161 and +3189 c.p.s. from trichlorofluoromethane. H nmr showed an aromatic multiplet [5] and a single at 85.52.  
 IR (cm. 1660 (s), 1610 (s), 1580 (m), 1450 (m), 1270 (s), 1170 (s), 1040 (w), 1020 (w), 1000 (w), 975 (w), 920 (s), 875 (w), 840 (m), 835 (w), 775 (m), 760 (m), 720 (s), 695 (s), 685 (s), 660 (w).  
 UV: In isooctane, sh 380 (e245) sh 325 (62690), 267  
  Mass spec. The most abundant ions were at m/e 343 and 239, suggesting predominant cleavage of the central carbon-carbon bond giving the stable dithiolium ions.  
  Analysis of the crude reaction mixture by nmr (the lines at 86.19 and 85.52) indicated that the two compounds were formed in a :70 ratio, respectively.  
 EXAMPLE 9 2-cinnamoyl-4,4 &#39;,5 ,5 &#39;-tetrakis(trifluoromethyl )-2 ,2 bi-(1,3-dithiole) (Formula 4; R&#39;=R =CF A mixture containing 16.5 g. of hexafluoro-Z-butyne, 24 g. of carbon disulfide, and 15 g. of cinnamaldehyde was heated at 100 for 3.5 days. The reaction product was concentrated under reduced pressure to remove excess carbon disulfide. Methanol was added to the residue, and it was cooled to to cause crystallization. Filtration gave 10.2 g. of 2-cinnamoyl-4,4&#39;-5,5&#39;- tetrakis(trifluoromethyl )-2,2 &#39;-di-( 1 ,3-dithio1e), which melted at 78-79. Recrystallization from hexane raised the melting point to 88.  
 Anal. Calcd. for C H F OS C, 37.50; H, 1.32; S, 21.08; F, 37.47 Found: C, 37.44; H, 1.49; S, 21.20; F, 37.51 F nmr showed two singlets of equal intensity at +3166 and +3187 c.p.s. from internal trichlorofluoromethane.  
 The product CF3-C-S\ CH-COCH=CHC6H5 CFa-C-S was also formed.  
 EXAMPLE l0 a-Methyl-4,5-bis(trifluoromethyl)- 1 ,3-dithiole-2- acetaldehyde (Formula 4; R=R =CF A mixture of 15 g. of propionaldehyde, 15 ml. of car bon disulfide, and 16.5 g. of hexafluoro-Z-butyne was heated at for 4 days. The reaction mixture was distilled under reducedpressure to give 8.1 g. of a-methyl- 4,5-bis(trifluoromethyl)-1 ,3-dithiole-2-acetaldehyde as a pale-yellow liquid, b.p. 54-5 5 at 0.25 torr, n 1.4428.  
 Anal. Calcd. for C H F OS C, 32.43; H, 2.04; S, 21.65; F, 38.48 Found: C, 32.34; H, 2.04; S, 21.61; F, 40.33  
 H nmr: Formyl C1-IO) hydrogen [1] as a broadened singlet at 89.40, dithiole hycrogen [1] as a doublet (J 6 c.p.s.) at 85.03, hydrogen multiplet [1], at 82.81 and a methyl [3] doublet (J 7 c.p.s.) at 81.24.  
 IR: Strong absoprtion at 1720 (carbonyl), 1620 (C-C double bond) and 1200 cm. (CF).  
  1 3 EXAMPLE 1 l 2-Acetonyl-4,5-bis(trifluoromethyl)-1 ,3-dithiole (Formula 4; R=R CF X=CH COCH EXAMPLE 12 a,a-Dimethyl-4,5-bis(trif1uoromethyl)- 1 ,3-dithiole- 2-acetaldehyde (Formula 4; R=R=CF CH 3 -C-CHO A mixture of 15 ml. of carbon disulfide, 15 ml. of isobutyraldehyde, and 16.5 g. of hexafluoro-Z-butyne was heated at 100 for 3 days. The reaction mixture was distilled through a short still head to give 9.0 g. of product, b.p. -50 at 0.6 torr, n 1.4400.  
 Anal. Calcd. for C H F OS C, 34.84; H, 2.60; S, 5  
 20.67; F, 36,74 Found: C, 35.07; H, 2.57; S, 19.85; F, 38.32  
 H nmr: Methyl singlet [6] at 81.17, methine singlet l at 85.08, and formyl hydrogen singlet [1] at 89.37.  
  EXAMPLE 13 2-(1-Methyl-2-oxopropyl)-4,5-bis(trifluoromethyl)- 1,3-dithiole (Formula 4; R=R ==CF E 3 X- -CH--COCII CFgC &#34;S I CH&#39;CH&#39;COCHS CF3C&#39;S A mixture of 15 ml, of carbon disulfide, 15 m1. of methyl ethyl ketone, and 16.5 g. of hexafluoro-2- butyne was heated at 100 for 4 days. Distillation of the reaction mixture gave 9.2 g. of 2-(l-methyl-2- &#39;oxopropyl)-4,5-bis(trifluoromethyl)-l,3-dithiole, b.p.  
 52-56 at 0.15 torr, r1 1.4443.  
 Anal. Calcd. for C H F OS C, 34.84; H, 2.60; S,  
  20.67; F, 36.74 Found: C, 34,92; H, 2.51; S, 20.76; F, 38.80 H nmr: Methyl doublet [3] centered at 81.14 (J 7 c.p.s.), methyl singlet [3] at 81.95, methine multiplet- [l] centered at 82.91, and a methine doublet [1] centered at 84.90 (J 8 c.p.s.).  
 EXAMPLE 14 2-(Diacetylmethyl)-4,5-bis(trifluoromethyl)-1,3- dithiole [Formula 4; R=R =CF X=CH(COCH ll CH-CH(COCH3 A sealed tube containing 15 ml. of carbon disulfide, 15 g. of 2,4-pentanedione, and 16 g. of hexafluoro-2- butyne was heated at 100 for 4 days. From the reaction mixture there was obtained 18.0 g. of 2- (diacetylmethyl)-4,5-bis(trifluoromethyl)-1,3-dithiole, m.p. 6869. Recrystallization from hexane raised the melting point to 7071.  
 Anal. Calcd. for C H F O S C,.35.50; 1-1, 2.39; S, 18.95; F, 33.70 Found: C, 35.71; H, 2.33; S, 19.31; F, 34.11  
 H nmr; Methyl singlet [6] at 82.33, and the methine hydrogens as an AB pattern [2] (J 11 c.p.s.) around 85.  
 IR: Carbonyl at 1700 and double bond at 1600 emf.  
 EXAMPLE l5 2-Benzoylmethyl-4,5-bis(trifluoromethyl)-l ,3-dithiole (Formula 4; R =R --CF X=CH COC H H CH&#39;CHgCOCcHs CF C-S A sealed tube containing 12 g. of acetophenone, 15 ml. of carbon disulfide, and 16.7 g. of hexafluoro-2- butyne was heated at 100 for 6 days. Filtration of the reaction mixture gave 28.3 g of 2-benzoylmethyl-4,5- bis(trifluoromethyl)-1,3-dithiole, m.p. 87. Recrystallization from hexane raised the melting point to 8788.  
 Anal. Calcd. for C H F OS C, 43.57; H, 2.25; S, 17.89; F, 31.81 Found: C, 43.91; H, 2.40; S, 18.01; F, 32.70  
 H nmr: Methylene doublet [2] centered at 83.65, methine triplet [1] centered at 85.20, and aromatic multiplet [5]. I  
 IR: Carbonyl absorption at 1700 cm..  
 EXAMPLE 16 2-(2-Oxocyclohexyl)-4,5-bis(trifluoromethyl)-1,3- dithiole (Formula 4; R =R CF CFaC&#39;S A mixture of 15 ml. of cyclohexanone, 15 ml. of carbon disulfide, and 17.2 g. of hexafluoro-Z-butyne was heated at 100 for days. The product was distilled through a short still head to give 25.2 g. of 2-(2- oxocyclohexyl)-4,5-bis(trifluoromethyl)-1,3-dithiole, b.p. 108 at 1.5 torr, n 1.4739.  
 Anal. Calcd. for C H F OS C, 39.28; H, 3.00; S, 19.07; F, 33.90 Found: C, 39.43; H, 3.22; S, 18.76; F, 34.40  
 H nmr: Broad absorption at 81 .03.0 [9] and a doublet centered at 85.12 [1] withJ 6 c.p.s.  
 EXAMPLE l7 MethyI-Z-diacetylmethyl-1 ,3-dithiole-4-carboxylate [Formula 4; R=CH COO; R =H; X=CH(COCH IT CH-CH( 000113 )2 Anal. Calcd. for C H O S C, 46.13; H, 4.64; S, 24.64  
 Found: C, 46.26; H, 4.60; S, 25.07  
 H nmr: Acetylmethyl [6] singlet at 82.28, methoxyl [3] singlet at 83.78, the methine hydrogens [2] as an AB pattern (J 11 c.p.s.) with chemical shifts at 84.60 and 5.48, and a dithiole hydrogen [1] singlet at 87.12.  
 EXAMPLE l8 2-[ l-(2-Methoxyl trifluoromethylcyclopropyl)trifluoroethylidene]-4,5- bis(trifluoromethyl)-l,3-dithiole (Formula 5; R=CF Y and Z together are criocH cr czccr cs cn ocn=ca era cm. cr q-s A mixture containing 18 g. of hexafluoro-2-butyne, 25.2 g. of carbon disulfide, and 19 g. of methyl vinyl ether was heated at 100 for 3.5 days. The product was distilled under reduced pressure through a spinningband column. 2-[ l-(2-Methoxy-1- trifluoromethylcyclopropyl)trifluoroethylidene]4,5- bis(trifluoromethyl)- 858 8 and 3.0 torr in a yield of 17.6 g. The center cut, b.p. 87.5 at 3.0 torr, r1 1.4291 (6.74 g.), was analyzed.  
 1,3-dithiole was collected at Anal. Calcd. for C, H F OS C, 31.5; H, 1.32; F, 49.8;  
 S, 14.0 Found: C, 32.0; H, 1.58; F, 49.9; S, 14.4  
  The H nmr spectrum clearly showed the presence of 5 two stereoisomers, corresponding to the 1,2- disubstituted cyclopropyl group. The cyclopropylmethylene resonance was a series of eight peaks [2] at the relatively high field position of 81.0 to 1.6. The methoxyl resonance was two peaks [3] at 86.6. The methine hydrogen (intensity 1) resonance occurred as four peaks, each split into a doublet atound 83.85.  
  The near-infrared specturm clearly showed the absorption at 6060 cm. characteristic of the cyclopropylmethylene group.  
 EXAMPLE l9 2-[ l-( 2-Ethoxyl -trifluoromethylcyclopropyl )trifiuoroethylidene]-4,5-bis(trifluoromethyl )-l ,3-dithiole (Formula 5; R =CF Y and Z together form A mixture containing 16.5 g. of hexafluoro-Z-butyne, 25 .2 g. of carbon disulfide and 14 g. of ethyl vinyl ether was heated at 70 for 6 days. Volatile liquids were removed under reduced pressure. The residue was filtered to give 0.69 g. of white solid which melted at 52-54. The filtrate was distilled to give 7.12 g. of product which boiled at 5 2-62 and 0.40 torr. The liquid (a mixture of stereoisomers of the dithiole shown above) and the solid (principally one isomer) had nearly identical infrared and nmr spectra. Recrystallization of the solid from hexane raised the melting point to 64-65.5. This recrystallized solid was analyzed. Anal. Calcd. for C H F Os z C. 33.1; H, 1.71; F, 48.3; S, 13.6; MW, 472 Found: C, 33.6; H, 1.86; F, 47.4; S, 13.8; MW (mass spec), 472  
 EXAMPLE 20 2-[ 1-( l-Trifluoromethylcyclopropyl)trifluoroethylidene]-4,5-bis(trifluoromethyl)-1,3-dithiole (Formula 5; R=CF Y and Z together form CF CFg CF c-s A mixture containing 17 g. of hexafluoro-Z-butyne, 18 g. of carbon disulfide, and 8 g. of ethylene was heated at for 5 days. It was distilled under reduced areas of resonance: A single peak at +3 209 c.p.s. [6],  
 pressure. 2-[ 1-( 1trifluoromethylcyclopropyl)- dithiole, 0.89 g., distilled at 42 and 20 torr, n  
 Anal. Calcd. for C H F S C, 30.9; H, 0.94; F, 53.2;  
 S, 15.0 Found: C, 32.4; H, 1.32; F, 51.4; S, 14.6  
 The H nmr spectrum of the product showed one broadened absorption at 83.1, corresponding to cyclo l0 propyl hydrogens.  
 &#39; EXAMPLE 21 2-[2-Acetoxy-bis-1,2-(trifluoromethyl)ethylidene]- 4,5-bis(trifluoromethyl)-1,3-dithiole (Formula 5;  
 era-g 111 C8; cnacoon a&#34; CF13 CFQ crsc -s l i 1 c=c Hococn (A) CFQC&#34;S I CFSC-S S-CCF 11 11 CF3C&#34;S &#39;SCCF A mixture of 15 ml. of acetic acid, 15 ml. of carbon disulfide, and 17.6 g. of hexafiuoro-Z-butyne was heated at 100 for 3 days. After the tube was cooled and opened, a small amount of gas evolved as the contents warmed to room temperature. The tube contents were poured into 250 ml. water. A red liquid separated and was extracted into ether. The ether solution was rinsed with water, dried over magnesium sulfate, and aspirated. The residue partly crystallized and was filtered to give 3.8 g. (16%) of the orange bi-dithiole (B) (described in Example 23, below), m.p. 85-89. The filtrate was concentrated under reduced pressure and the residue was distilled to give 16.9 g. (73%) of 2-[2- acetoxybis-l ,2-(trifluoromethyl)ethylidene]-4,5-bis- (trifluoromethy1)-1,3-dithiole, (A), b.p. -48 at 0.3 torr, n 1.4202.  
 Anal. Calcd. for C H F O S C, 28.70; H, 0.88; F, 49.54; S, 13.93 Found: C, 28.76; H, 0.82; F, 49.43; S, 15.12  
 H nmr; Methyl [3] at 81.98 and a hydrogen [1] as a quartet (J 7 c.p.s.) centered at 85.73. F nmr calibrated from trichlorofluoromethane showed three EXAMPLE 22 2-[2-Benzoyloxy-l,2-bis(trifluoromethyl)ethylidene]- 6Q CF CF C=C CHOCOC H5 CF C- A mixture of 17 g. of hexafluoro-2-butyne, 25 ml. of carbon disulfide, ml. of ethyl ether, and 15 g. of benzoic acid was heated at for 8 hours. The pale red solution was dissolved in 300 ml. of ether. The solution was extracted with aqueous sodium carbonate solution to remove unchanged benzoic acid, dried over magnesium sulfate, filtered, and concentrated on a rotary evaporator. The residual oil crystallized upon standing overnight. Filtration gave 19.4 g. (73%) of 2- ]2-benzoyloxy-1,Z-bis-(trifluoromethyl)ethylidene]- 4,5-bis(trifluoromethy1)-l,3-dithiole which melted at 53-55. Recrystallization from methanol raised the melting point to 62-63.  
 Anal. Calcd. for C H F O S C, 36.79; H, 1.16; S, 12.28; F, 43.65 Found: C, 37.13; H, 1.25; S, 12.77; F, 43.65  
 Hnmr: Aromatic multiplet [5] at 87.3 to 8.2 and a CH quartet [1] centered at 86.14 (J 7 c.p.s.).  
 R nmr: Three areas: A [6] a complex multiplet centered at +3156 c.p.s from trichlorofluoromethane; B [3] a quartet centered at +3478 c.p.s., J=10 c.p.s.; C [3] a quartet split into doublets centered at +4183 c.p.s., J, 10 c.p.s., J 7 c.p.s.-  
 IR: 1650 cm. (carbonyl), 1600 and 1540 cm.  
 (C=C), and 1260 and 1180 cm. (CF).  
 EXAMPLE 23 4,4 &#39;,5 ,5 &#39;-Tetrakis(trifluoromethyl -bi-(l,3-dithiole) (Formula 1; R=R CF FSCECCF cs CF CF3C&#39;S s-ccr l c-c I] CF30 &#34;S S &#34;CCF;  
 Annal. Calcd. for C F S C, 25.2; F, 47.9; S, 26.9 MW, 476 Found: C, 25.5; F, 47.8; S, 27.2; MW (mass spec.), 476  
 Mass spec.: In addition to the parent peak there was an abundant peak at m/e 238 (half parent).  
 UV: ln isooctane, A 412 (61520), 310 (613,600)  
 and 222 m (612,600).  
 F nmr: One single sharp peak at 578 c.p.s. from external 1,2 difiuorotetrachloromethane.  
 IR: Strong carbon-carbon double-bond absorption at Heating the reactants in the absence of the acid gave a low (2%) yield of the above product. In the presence of acetic acid (pK 4.76; Example 21) the yield of the bi-dithiole was 16%. With formic acid (pK 3.75) the yield was 50%.  
 EXAMPLE 24 Tetramethyl- -bi-( 1,3-dithiole )-4,4&#39;,5 ,5 &#39;-tetracarboxylate (Formula 1; R=R =CH COO) C113 oocc -s s-ccooca n c=c ll cna ooc-c-s s-ccoocn A mixture of 14.2 g. of dimethyl acetylenedicarboxylate, 25.2 g. of carbon disulfide, and 22 g. of acetic acid was heated at 100 for four days. The mixture was filtered to give 2.1 g. of the bi-dithiole, m.p. 165168. Recrystallization from benzene-hexane raised the melting point to 169170.  
 Anal. Calcd. for C I-1 0,5 C, 38.5; H, 2.77; S, 29.4  
 Found: C, 38.8; H, 2.83; S, 29.3  
  The nmr spectrum of the product Showed nly 15 IR: Carbon-carbon double-bond absorption at 1575 .1. St CF bso t&#39;on at 1150 and 1250 one peak, at 83.85. The infrared spectrum showed carz$ long a rp l bonyl absorption at 1710 and 1740 cm. and carbon- UV: Mm 288 nm (516,500) in isooctane carbon double bond absorption at 1570 cm.&#39;. The ultraviolet spectrum (ethanol) Showed absorption at 445 The hexane filtrate from above was concentrated and (51930) 315 (l3100) 284 (614300) and 245 nm the residue was refiltered to give 8.15 g of amorphous (E155 solid. The ether-insoluble and hexane-soluble parts EXAMPLE were separated from the bulk of the solid (7.05 g. mp I I 25 105112C), which was soluble in ether or hexane but Dlethyl bl-(1 &#39;dlcarboxylate insoluble in methanol. A small amount of this material (.A); P was sublimed, and the sublimate melted at 1 l9-121C. A &#39;dlcarboxylate (B) The infrared spectrum of the sublimate was identical to that of l,1,1,4,4,4-hexafluoro-2,3-butadiylidene)- HC-S S-CH 2,2-bis[4,5-(trifluoromethyl)-1,3-dithiole], described CrzC by Krespan and England, J. Org. Chem. 33, 1853-1854 cu cn ooc-s s-c-coocn ca (1968)- When a mixture of 16.8 g. of the hexafluoro-Z-butyne and 50.4 g. of carbon disulfide was similarly heated, a z a yield of 12.8 g. (60%) of the product of Formula 2 ll l (B) (R R =CF was obtained. C11 CH OOC-S S-C a H EXAMPLE 27 Tetramethyl 3.15332&#34;???$ 3,533:;-  
  th di l&#39;dene -2,2 -bis 1,3-dithio e- ,5- which is either one of the two geometric isomers (A) j sgiylgt e) (Fgrmula 2 (R =R =COOCH3) and (B), possibly contaminated with the other isomer. The product melted at 130-l44. Recrystallization from methanol raised the melting point to 169172. COOCHS COOCHS CH OOCC-S Anal. Calcd. for C, H O S.,: C, 41.3; H, 3.47; S, 36.8 3 n C: s S  
  Found: C, H, S, The H nmr spectrum showed a methyl triplet [3] centered at 81.35, a methylene quartet [2] centered at COOCH; 000C11 64.31, a methine singlet [l] at 87.40.  
  EXAMPLE 26 s-Tetrathianediylidenedi-[bis(trifluoromethyl)ethane- S&#39;CCOOCH3 diylidene]-2,2-bis[4,5-bis(trifluoromethyl)-1,3- C  
 dithiole] (Formula 2; R=R =CF S-CCOOCH cr czccr C3:  
 QF CFQ CF CF CF C-S tetrathianediylidenedi- [bis(trifluoromethyl)ethanediylidene]-2,2&#39;-bis[4,5-  
 bis(trifluoromethyl)-1,3-dithiole] which melted at 177. Recrystallization from acetone gave white crystals of the product which melted at when immersed in a preheated bath.  
 Anal. Calcd. for C F S C, 25.2; F, 47.9; S, 26.9; MW, 932 Found: C, 25.1; F, 48.0; S, 28.0; MW, 921  
 (cbullioscopic in acetone) A mixture of 14.2 g. of dimethyl acetylenedicarboxylate and 50.4 g. of carbon disulfide was heated at 100 for 18 hours. The mixture was filtered to give 1.11 g. of solid tetramethyl s-tetrathianediylidenedi[bismethoxycarbonyl)ethanediylidene]-2,2 &#39;-bis( 1 ,3- dithiole-4,5-dicarboxylate) which melted at 237239 with decomposition. Recrystallization from diethylene glycol dimethyl ether raised the melting point to 247-250 with decomposition.  
 Anal. Calcd. fOr C28H24016S8: C, H, S, Found: C, 38.9; H, 3.04; S, 29.1  
 IR: Carbonyl absorption at 1750, 1740, and 1720 cmfl. Carbon-carbon double-bond absorption at 1550 cmfl.  
 EXAMPLE 28 Tetramethyl bis(methoxycarbonyl)ethanediylidene-2,2 -bis-( 1,3-  
 CH OOCC ECCOOCIL CS COOCHg COOCI-l -CH3OOC-C-S l C=C C: CH3OOC-C-S s-ccooca s-ccoocu Anal. Calcd. for C d-1 0 8 C, 41.5; H, 3.14; S, 22.2;  
 dithio1e-4,5-dicarboxylate) (Formula 3; 25 MW, 578 Found: c, 41.6; H, 3,3; s, 22,3; MW, 578  
 R1=R2=COOCH3) (mass spec) Mass Spectrum m1 Intensity I Assignment 578 6539 Parent 5 17 471 P ocna 519 3 3 P COOCH 160 399 P 2 coocn casooc c-s 372 28.5 P 1 ca ooc-c-s CH3OOCC-S 360 20.1 P u c cmooc-c-s coocna ca ooc-c-s l 289 531.1 l/2P, i.e., h c=c- Acetone Solution Compound, (Example) lml) CFa-C-S S- C- CF l C=C 0.27 (25) 1O CF c-s sc-cra CF15 CF3 CF3 CFQ CF3-C-S ,SS SCCF3 2 C=C C C C=C C=C 2O cr -c-s s-s S-C-CF CF13 CFa CFa-C-S SC-CF 3 c-c c=c .08 (26) 5 CF -C-S s-c-cr CF3-C-S 4. CH-CHgCOCHs 0.12 5  
 crsc-s CF3 CF CFg-C-S 5 c=c c CH-OCH 0.7 (18) 5 crs-c-s CH Each solution was tested by dipping a cloth into it in which and then rubbing a tarnished silverware fork with the R is a member of the group alkoxycarbonyl of up to wetted area. In each test the wetted cloth removed the 12 carbon atoms, aryloxycarbonyl of up to 13 cartarnish and improved the appearance of the silver. In bon atoms, lower perfluoroalkyl, arylcarbonyl of a similar test with a cloth wetted only with acetone, the up to 13 carbon atoms, or the cyano group; and tarnished silver remained unchanged in appearance. R is either the same as R or hydrogen, C -C alkyl, The embodiments of the invention in which an excluaryl of up to 12 carbon atoms, or aralkyl of up to sive property or privilege is claimed are defined as follows:  
  l. A process for the preparation of a mixture of compounds having the following formulas (1), (2) and (3):  
  2. A process of claim 1, leading predominantly to the product of formula (3), wherein the starting molar ratio of carbon disulfide to the acetylenic compound is at least about 5:1.  
  3. A process of claim 1, leading predominantly to the compound of formula(2), wherein the starting molar ratio of carbon disulfide to the acetylenic compound is less than about 5:1.  
  4. A process of claim 1, wherein the temperature is maintained within the range of about -l50C. 5. A compound having the following formula R is a member of the group alkoxycarbonyl of up to 12 carbon atoms, aryloxycarbonyl of up to 13 carbon atoms, lower perfluoroalkyl, arylcarbonyl of up to 13 carbon atoms, or the cyano group; and  
 R is either the same as R or hydrogen, a C -C alkyl, aryl of up to 12 carbon atoms, or alkaryl of up to 12 carbon atoms.  
 R is a member of the group alkoxycarbonyl of up to 12 carbon atoms, aryloxycarbonyl of up to 13 carbon atoms, lower perfluoroalkyl, arylcarbonyl of up to 13 carbon atoms, or the cyano group; and  
 R is either the same as R or hydrogen, a C -C alkyl, aryl of up to 12 carbon atoms, or alkaryl of up to 12 carbon atoms.  
 7. A compound having the folowing formula C S R S C R R n t C R CS S-G-R in which R is a member of the group alkoxycarbonyl of up to 12 carbon atoms, aryloxycarbonyl of up to 13 carbon atoms, arylcarbonyl of up to 13 carbon atoms, or the cyano group; and R is either the same as R or hydrogen, a C -C alkyl, aryl of up to 12 carbon atoms, or alkaryl of up to 12 carbon atoms. 8. A process for the preparation of a compound of the formula R-c-s s- R- -s \SC-R2 inwhich R is a member of the group alkoxycarbonyl of up to 12 carbon atoms, cycloxycarbonyl of up to 13 carbon atoms, lower perfluoroalkyl, arylcarbonyl of up to l3 carbon atoms, or the cyano group; and  
 R is either the same as R or hydrogen C -C alkyl, aryl of up to 12 carbon atoms or aralkyl of up to 12 carbon atoms,  
 said process comprising the step of contacting a mixture consisting essentially of an acetylenic compound having the formula RC I CR in which R and R having the above-defined meaning, with carbon disulfide, and a lower alkanoic acid or haloalkanoic acid having a p Ka of less than about 5 in an amount of 0.1 to 3 moles per mole of said R C IE CR at a temperature in the range of 30200C.  
 9. A process of claim 8 wherein the temperature is maintained within the range of about -l50C.