ARTICLE

Synthesis of novel ([oligomethylene]alkane-�,�-diyl)bis(diallylcarbamodithioates); monomers as precursors forRAFT photoplastic polymer networksCornelis M. Moorhoff, Wayne D. Cook, and Carl Braybrook

Abstract: An efficient three-component coupling reaction of N,N-diallylamine, carbon disulfide, and bis(allyl chlorides) of thetype �,�-bis(chloromethyl)poly(glycolyl)-�,�-dienes and other such compounds, in the presence of excess triethylamine inchloroform, has been established. The resulting mixtures gave after aqueous workup novel ([oligomethylene]alkane-�,�-diyl)bis(diallylcarbamodithioates) that may also function as useful monomers for RAFT-based photoplastic polymer networks.

Key words: bis(diallylcarbamodithioates), photoplastic polymer networks, �,�-bis(chloromethyl)poly(glycolyl)-�,�-dienes,([oligomethylene]alkane-�,�-diyl) bis(diallylcarbamodithioates).

Résumé : On a mis au point une réaction efficace de couplage a trois composés entre N,N-diallylamine, disulfure de carbone etbis(chlorures d’allyle) de type �,�-bis(chlorométhyl)poly(glycolyl)-�,�-diènes et d’autres composés de ce genre, en présence d’unexcès de triéthylamine dans du chloroforme. Le mélange résultant a donné, après extraction en phase aqueuse, de nouveaux([oligométhylène]alkane-�,�-diyl)bis(diallylcarbamodithioates) qui peuvent aussi fonctionner comme des monomères utilespour les réseaux de polymères photoplastiques obtenus par polymérisation de type RAFT. [Traduit par la Rédaction]

Mots-clés : bis(diallylcarbamodithioates), réseaux de polymères photoplastiques, �,�-bis(chlorométhyl)poly(glycolyl)-�,�-diènes,([oligométhylène]alkane-�,�-diyl)bis(diallylcarbamodithioates).

IntroductionPolymers that exhibit photoplasticity1–16 are a novel type of

stimuli responsive polymers where UV (or visible) radiation caninduce shape change or stress relaxation in a chemically cross-linked polymer only during the radiation period. Such polymersmay be useful for photo-activated actuators3,4,5,9 or for self-healing of fractured polymers13,14,16 or they may reduce internalstresses that may develop in crosslinked polymers as a result ofshrinkage during polymerization.6,9 Several years ago,10 we col-laborated in the development of novel photoplastic networksformed from the thiol-ene reaction of a tetra thiol crosslinkingmonomer, pentaerythritol tetrakis(3-mercaptopropionate) (PETMP)1, with 2-methylenepropane-1,3-di(thioethyl vinyl ether) (MDTVE)2.9,10 In the latter case, the crosslinked 3D polymer network 3 andschematically abbreviated as 4 (Scheme 1) was formed. Using oneradical photo-initiator that absorbed in the visible spectrum toinitiate the thiol-ene reaction and another that only absorbed inthe UV spectrum, we were able to form a crosslinked polymer thatunderwent shape change on irradiation with UV radiation.

The unique photoplastic behaviour of such a cured thiol-enenetwork 3 lies within the allylic dithioether or (2-methylenepropane-1,3-diyl) bis(sulfandiyl) moiety 5 of the network strands (Scheme 1).The detailed photoplastic mechanism involving this subunit 5 canbe explained when it is recognised that a photogenerated carbonradical, R•, attacks the terminal alkene carbon C1 of 5 to form atertiary radical that breaks down to a new allylic group betweeneither C2 and C3 or C2 and C3= (or even reformation of the originalallylic group) and �-cleavage of the C3−S bond or C3=−S bond and

the formation of a new sulfanyl radical R=S• or R==S• (Scheme 1, 5bor 5a). This new sulfanyl radical is then able to attack anotheralkene at a neighbouring polymer chain, again causing �-scissionand the creation of another sulfanyl radical. Thus, the networkchains are broken and reformed in new configurations so that anystress that had been imposed on the chains can be released andshape change can occur.

We have also studied the photoplasticity of diepoxide networkscontaining the moiety 5 in the backbone15 and Amamoto et al.have studied the photo-induced healing of networks containingthe related trithiocarbonate unit.14,16 As an alternative, we areinvestigating monomers containing bis(allyldithiocarbamate) groupsand the synthetic work on this is recorded here. Radical cyclo-polymerizations, initiated by TiC13/H202 or AIBN, of N,N-diallylmonomers 6 (Scheme 2) can result in polymers of two structuraltypes, namely, polymers having repeating units containing five-membered rings leading to pyrrolidine polymers 7 when unsub-stituted allyl groups (R = H) of monomers 6 are used17,18 and thiswas confirmed by NMR studies.19 Thus, AIBN-induced radical cy-clopolymerization of N-methyl-N,N-diallylamine (6) (R = H, R== =Me) gave exclusively the pyrroline type polymer 7 in a cis:transratio of 5:1.19 However, when the allyl groups are substituted(R = alkyl), then due to steric hindrance, the more stable six-membered piperidine polymer 8 will form.20,21 It must be notedthat even though diallylamines can be free radically polymerized,the reaction is slow and results in low molecular weight polymers.However, protonation or alkylation of the amine to form the qua-ternary cation results in a more rapid polymerization.

Received 15 September 2013. Accepted 4 October 2013.

C.M. Moorhoff and W.D. Cook. Department of Materials Engineering, Monash University, Clayton, VIC 3800, Australia.C. Braybrook. Materials Science and Engineering, CSIRO, Clayton, VIC 3169, Australia.Corresponding author for Synthesis: Cornelis Moorhoff (e-mail: cornelis.moorhoff@monash.edu); Corresponding author for Photoplasticity:Wayne Douglas Cook (e-mail: wayne.cook@monash.edu).

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Can. J. Chem. 92: 19–25 (2014) dx.doi.org/10.1139/cjc-2013-0426 Published at www.nrcresearchpress.com/cjc on 15 October 2013.

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In this report, we describe the synthesis of a number of noveldiallyldithiocarbamate monomers, some having multiple allylicdithioether moieties 5 embedded in the monomer, as is a require-ment for photoplasticity. Our goal in doing this is to preparecrosslinked polymers that have longer chains and several allylicdithioether moieties 5 to further enhance the speed and extent ofphotoplasticity in the polymers.

Results and discussionWe recently have reported the synthesis of monomers having

one allylic dithioether moiety 5 with two epoxide end-groups as

the polymerizable unit for photoplastic polymer preparations.22

We have also reported the synthesis of compounds where two vinylethers end-groups were used as polymerizable units, but having notone but two allylic dithioether moieties 5.23 Very few examplesare available about the preparation of diallylcarbamodithioatemonomers containing additional unsaturated groups,24 and forbis(allylcarbamodithioates), the information is even more scarce,25,26

for example, the 2-butenylene ester of diallyldithiocarbamic acidhas been prepared and used for the preparation of organome-tallic complexes.25 Our general approach to the preparation ofbis(diallylcarbamodithioates) 11 (Scheme 3) is based on the litera-ture procedure by Azizi et al.24 in which CS2 and primary or sec-ondary amines were reacted with activated chlorides over severalhours at room temperature. This synthesis was claimed to be a“green-method”, since no solvent was used. However, CS2 wasused in excess, and apart from its stench, it is highly flammable andtoxic. In addition, for our synthesis of bis(diallylcarbamodithioates),the diallyl amine would have to be used in excess but it is expen-sive. Thus, we modified the method of Azizi et al.24 and used only1 mol equiv. of CS2 and 1 mol equiv. of diallylamine per halogen,and we used an excess of the inexpensive triethylamine to removeHCl as its trialkylammonium salt, which is easily extracted fromthe organic mixture into water. Thus, 2 equiv. of diallylamine 9should react with a mixture of bis(allyl chloride) 10 and 2 mol equiv.of CS2 to form 11 (Scheme 4). It was anticipated that these mono-mers could be radically polymerized (perhaps in an acidic me-dium) to form a 3D polymer network 12 having the pyrrolidinestructure as the repeating unit (Scheme 4). With the addition of aphotoinitiator in the monomer before its polymerization, irradi-

Scheme 1. Thiol-ene photoplastic polymer networks.

Scheme 2. Polymerization of an N,N-allylamine 6 and the formationof pyrrolidine polymer 7 and (or) piperidine polymer 8.

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ation of the crosslinked polymer with the appropriate wavelengthcould form radicals that would start the chain scission processshown in Scheme 2 leading to the photoplasticity effect as ex-plained in the Introduction.

In our first example, we used 3-chloro-2-chloromethyl-1-propene 10aas a substrate with CS2, diallylamine, and excess triethylamine inan attempt to form the bis(diallylcarbamodithioate) 11a. In theabsence of a solvent, the strong exothermic reaction partiallyevaporated the low-viscosity but volatile CS2 (bp 46 °C) and thisprevented efficient stirring and thus adequate mixing, leadingto incomplete reaction. Use of dichloromethane as solvent wasfound to also react with CS2 and diallylamine to form the simplebis(diallylcarbamodithioate) 13 (Scheme 3), and the nucleophilicdisplacement reaction by sulfur on dichloromethane is wellknown.27–31 Tetrahydrofuran as a solvent, as suggested by Aziziet al.,24 led to unwanted yellow impurities.

We then performed the reactions in chloroform and found it tobe an ideal solvent that was not attacked by the sulfur nucleo-phile. Thus, a mixture of 10a and CS2 in chloroform was added toa stirring solution of diallyl amine and excess triethylamine inchloroform at room temperature. The reaction was exothermicand within 5 min, triethylammonium hydrochloride precipita-tion could be seen. However, chloroform does partially dissolvetriethylammonium hydrochloride and aqueous extraction is

therefore important for the total removal of this ammonium salt.The product 11a was then isolated in good yield and high purity. Aseries of bis(diallyldithiocarbamates) 10 were then synthesizedfrom the known precursors 10b,22 10c,22 10d,22 10e,22 10f,32

10g,32 10h,22 and 10i32 (Scheme 5) (Fig. 1) in the same manner asfor 11a to form the expected products 11b, 11c, 11d, 11e, 11f, 11g,11h, and 11i in good to high yields (Scheme 5).

Compound 11a is very yellow, but as the �- and �-diallylcarbamodithioate groups are increasingly separated, thecolour becomes less intense so that 11f and 11g are only paleyellow and 11h is near colourless.

An investigation into the photopolymerization and photo-plastic properties of the crosslinked polymers derived frombis(diallylcarbamodithioates) 11 is in progress and will be re-ported elsewhere.

Experimental3-Chloro–2-chloromethyl-1-propene 10a was purchased from

Secant Chemicals Inc. All other chemicals were purchased fromAldrich. None of the chemicals purchased were purified. Chloro-form was dried with 4 Å molecular sieves for 24 h before use. NMRspectra were obtained with Bruker 300 and 400 MHz instrumentsin CDCl3 with its residual chloroform peak at 7.25 ppm as the as a

Scheme 3. Preparation of bis(diallylcarbamodithioate) 11a.

Scheme 4. Bis(diallylcarbamodithioate) 11 and the 3D polymer network 12.

Moorhoff et al. 21

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reference in proton NMR and 77.0 ppm in carbon NMR as a refer-ence. EI or ESI mass spectra were obtained as indicated; for moredetails, consult the Supplementary material section.

General procedure for the preparation and purification ofbis(diallyldithiocarbamate) compounds (5–10 mmol scale)

A mixture of CS2 (>2 equiv.) and bis(allyl chloride) (1 equiv.) inchloroform (1 mL) was added, within 1 min, to a stirring mixture ofdiallylamine (2 equiv.) and triethylamine (5 equiv.) in chloroform(2 mL) at 0 °C. The reaction became yellow and was then stirred for5 h at �40 °C. A precipitate of triethylammonium hydrochloride

formed slowly; however, most of the salt remained dissolved inchloroform. The reaction mixture was then treated with water(20 mL) and neutralised with aqueous 4 mol/L HCl solution (usingpH paper) before being extracted twice with dichloromethane(20 mL). The combined dichloromethane fraction was then washedwith water (pH paper) and dried with Na2SO4. The dried extractwas filtered over a 5 mm bed of silica gel in a 20 mm diameterHirsch funnel and the filtrate rotary evaporated. Traces of solventwere removed at 60 °C under high vacuum to give a yellow viscousoil of the bis(diallyldithiocarbamate) compound.

Scheme 5. Activated bis(allyl chlorides) 10 used for the preparation of bis(diallylcarbamodithioates) 11. i: CS2 and diallylamine in chloroformin the presence of excess Et3N.

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(2-Methylenepropane-1,3-diyl)bis(diallylcarbamodithioate) (11a)Unoptimised yield: 66%. 1H NMR (200 MHz) �: 4.14 (s, 4H,

SCH2), 4.34 and 4.64 (2 × brs, 8H, NCH2CH=CH2), 5.17 (s, 2H,SCH2C=CH2), 5.25 (d, J = 17.1, 4H, NCH2CH=CH2), 5.24 – 5.28 (m,4H, NCH2CH=CH2), 5.84 (brs, 4H, NCH2CH=CH2). 13C NMR (CDCl3) �:42.6 (2 × CH2S), 54.0 and 56.9 (4 × NCH2), 118.8 (4 × CH=CH2), 118.9(C=CH2), 130.8 and 131.4 (4 × CH=CH2), 139.8 (C=CH2), 197.8 (2 × C=S)ppm. m/z (EI): 398 (1%, M+), 312 (2%), 226 (100%), 172 (13%), 140 (14%),73 (12%), 55 (3%). HRMS calcd. for [C18H26N2

32S4]: 398.0973; found:398.0980. FT-IR (neat) � = 3080 (w), 3010 (w), 2981 (w), 2908 (m),1640 (m), 1464 (s), 1429 (m), 1395 (vs), 1335 (m), 1275 (w), 1223 (vs),1168 (s), 1124 (m), 1098 (m), 1067 (w), 990 (m), 964 (w), 910 (vs), 683 (m),643 (m), 551 (m) cm−1.

(2,2=-[2,2=-Oxybis{ethane-2,1-diyl}bis{sulfanediyl}]bis(methylene)bis[prop-2-ene-2,1diyl]) bis(diallylcarbamodithioate) (11b)

Yield: 82%. 1H NMR (CDCl3) �: 2.61 (t, J = 6.8, 4H, OCH2CH2S), 3.25(d, J = 0.8, 4H, SCH2C=), 3.58 (t, J = 6.8, 4H, OCH2CH2S), 4.15 (d, J =0.8, 4H, S=CSCH2C=), 4.32 and 4.63 (2 × brs, 8H, NCH2CH=CH2),5.07 (d, J = 0.8, 2H, C=CH2), 5.18 (d, J = 17.6, 4H, NCH2CH=CH2), 5.23(d, J = 1.2, 2H, C=CH2), 5.2 – 5.3 (m, 4H, NCH2CH=CH2), 5.8 (brs,4H, NCH2CH=CH2). 13C NMR (CDCl3) �: 30.5 (2 × OCH2CH2S), 37.2(2 × SCH2C=), 41.1 (2 × CH2SC=S), 53.6 and 56.6 (2 × br, 4 ×NCH2CH=CH2), 70.3 (2 × CH2O), 117.2 (2 × =CH2), 118.5 (4 ×NCH2CH=CH2), 130.5 and 131.1 (2 × brs, 4 × NCH2CH=CH2), 139.5(2 × C=CH2), 197.5 (2 × C=S). HRMS (ESI) [M+Na]+ calcd. for[C26H40N2O32S6Na]+: 611.1363; found: 611.1368. FT-IR (neat) � =3077 (w), 2980 (w), 2911 (w), 2855 (w), 1639 (m), 1464 (s), 1426 (m),

1395 (vs), 1350 (m), 1275 (m), 1224 (vs), 1170 (s), 1098 (s), 991 (s), 965 (m),907 (vs), 739 (m), 646 (m), 551 (m) cm−1.

(2,15-Dimethylene-7,10-dioxa-4,13-dithiahexadecane-1,16-diyl)bis(diallylcarbamodithioate) (11c)

Unoptimised yield: 62%. Rf (100% EtOAc on silica gel) = 0.71.1H NMR (CDCl3) �: 2.62 (t, J = 6.8, 4H, OCH2CH2S), 3.25 (d, J = 0.8, 4H,SCH2C=), 3.59 (s, 4H, CH2O), 3.62 (t, J = 6.8, 4H, OCH2CH2S), 4.15 (d,J = 0.8, 4H, S=CSCH2C=), 4.32 and 4.64 (2 × brs, 8H, NCH2CH=CH2),5.07 (d, J = 1.2, 2H, C=CH2), 5.19 (dm, J = 17.6, 4H, NCH2CH=CH2), 5.22 (d,J = 1.2, 2H, C=CH2), 5.23–5.28 (m, 4H, NCH2CH=CH2), 5.75–5.93 (m, 4H, NCH2CH=CH2). 13C NMR (CDCl3) �: 30.4 (2 ×OCH2CH2S), 37.2 (2 × SCH2C=), 41.1 (2 × CH2SC=S), 53.6 and 56.6 (2 ×br, 4 × NCH2CH=CH2), 70.3 and 70.7 (4 × CH2O), 117.2 (2 × =CH2),118.5 (4 × NCH2CH=CH2), 130.5 and 131.1 (2 × br, 4 × NCH2CH=CH2),139.5 (2 × C=CH2), 197.3 (2 × C=S). HRMS (ESI) [M+Na]+ calcd. for[C28H44N2O2

32S6Na]+: 655.1625; found: 655.1617. FT-IR (neat) � =3079 (w), 2979 (w), 2910 (m), 2861 (m), 1639 (m), 1465 (s), 1396 (vs),1350 (m), 1275 (m), 1225 (vs), 1170 (s), 1098 (vs), 991 (s), 965 (m),906 (vs), 736 (m), 694 (m), 648 (m), 552 (m) cm−1.

(2,12,22-Trimethylene-7,17-dioxa-4,10,14,20-tetrathiatricosane-1,23-diyl) bis(diallylcarbamodithioate) (11d)

Yield: 84%. 1H NMR (CDCl3) �: 2.59 (t, J = 6.8, 4H, OCH2CH2S), 2.61(t, J = 6.8, 4H, OCH2CH2S), 3.25 (d, J = 0.8, 4H, SCH2C =), 3.31 (s, 4H,SCH2C=), 3.57 (t, J = 6.8, 4H, OCH2CH2S), 3.58 (t, J = 6.8, 4H,OCH2CH2S), 4.15 (d, J = 0.8, 4H, S=CSCH2C=), 4.31 and 4.63 (2 × brs,8H, NCH2CH=CH2), 5.00 (s, 2H, C=CH2), 5.07 (d, J = 1.2, 2H, C=CH2), 5.18

Fig. 1. The 1H NMR and 13C NMR of compound 11g in CDCl3 measured at 30 °C.

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(dm, J = 17.6, 4H, NCH2CH=CH2), 5.22 (d, J = 1.2, 2H, C=CH2), 5.20–5.27 (m, 4H, NCH2CH=CH2), 5.75–5.93 (m, 4H, NCH2CH=CH2).13C NMR (CDCl3) �: 30.4, 30.5 (4 × OCH2CH2S), 35.7 (2 × SCH2C=),37.2 (2 × SCH2C=), 41.0 (2 × CH2SC=S), 54.5 and 56.5 (2 × brs, 4 ×NCH2CH=CH2), 70.3 (2 × CH2O), 70.3 (2 × CH2O), 115.9 (=CH2), 117.2(2 × =CH2), 118.5 (4 × NCH2CH=CH2), 130.4 and 131.0 (2 × brs, 4 ×NCH2CH=CH2), 139.5 (2 × C=CH2), 140.8 (C=CH2), 197.4 (2 × C=S).HRMS (ESI) [M+Na]+ calcd. for [C34H54N2O2

32S8Na]+: 801.1849; found:801.1874. FT-IR (neat) � = 3078 (w), 2950 (w), 2912 (m), 2854 (m),2788 (w), 1639 (m), 1465 (s), 1396 (vs), 1353 (m), 1267 (m), 1225 (vs), 1170 (s),1096 (vs), 992 (m), 965 (w), 906 (vs), 739 (m), 646 (m), 552 (m) cm−1.

(2,15,28-Trimethylene-7,10,20,23-tetraoxa-4,13,17,26-tetrathianonacosane-1,29-diyl) bis(diallylcarbamodithioate) (11e)

Yield: 75%. Rf (100% EtOAc) = 0.68. 1H NMR (CDCl3) �: 2.60 (t, J =6.8, 4H, OCH2CH2S), 2.62 (t, J = 6.8, 4H, OCH2CH2S), 3.25 (d, J = 0.8,4H, SCH2C=), 3.30 (s, 4H, SCH2C=), 3.59 (s, 8H, CH2O), 3.60 (t, J =6.8, 4H, OCH2CH2S), 3.61 (t, J = 6.8, 4H, OCH2CH2S), 4.15 (d, J = 0.8, 4H,S=CSCH2C=), 4.32 and 4.63 (2 × brs, 8H, NCH2CH=CH2), 4.99 (s,2H, C=CH2), 5.07 (d, J = 1.2, 2H, C=CH2), 5.18 (dm, J = 17.6, 4H,NCH2CH=CH2), 5.25 (d, J = 1.2, 2H, C=CH2), 5.23–5.28 (m, 4H,NCH2CH=CH2), 5.75–5.92 (m, 4H, NCH2CH=CH2). 13C NMR (CDCl3)�: 30.4 (4 × OCH2CH2S), 35.7 (2 × SCH2C=), 37.3 (2 × SCH2C=), 41.1 (2 ×CH2SC=S), 53.6 and 56.6 (2 × brs, 4 × NCH2CH=CH2), 70.3 (4 × CH2O),70.6 (2 × CH2O), 70.7 (2 × CH2O), 115.9 (=CH2), 117.2 (2 × =CH2), 118.5(4 × NCH2CH=CH2), 130.1 and 131.3 (2 × brs, 4 × NCH2CH=CH2), 139.5(2 × C=CH2), 140.9 (C=CH2), 197.5 (2 × C=S). HRMS (ESI) [M+Na]+

calcd. for [C38H62N2O432S8Na]+: 889.2373; found: 889.2384. FT-IR

(neat) � = 3079 (w), 2911 (m), 2860 (m), 1640 (m), 1467 (s), 1397 (vs),1350 (m), 1275 (m), 1226 (vs), 1171 (m), 1096 (vs), 992 (s), 908 (vs),736 (m), 645 (m), 551 (m) cm−1.

(2,12,22,32-Tetramethylene-7,17,27-trioxa-4,10,14,20,24,30-hexathiatritriacontane-1,33-diyl) bis(diallylcarbamodithioate) (11f)

Yield: 78%. 1H NMR (CDCl3) �: 2.59 (t, J = 6.8, 8H, OCH2CH2S), 2.61(t, J = 6.8, 4H, OCH2CH2S), 3.25 (d, J = 0.8, 4H, SCH2C=), 3.31 (s, 8H,SCH2C=), 3.57 (t, J = 6.8, 8H, OCH2CH2S), 3.58 (t, J = 6.8, 4H,OCH2CH2S), 4.15 (d, J = 0.8, 4H, S=CSCH2C=), 4.35 and 4.63 (2 ×br-s, 8H, NCH2CH=CH2), 5.00 (s, 4H, C=CH2), 5.07 (d, J = 1.2, 2H,C=CH2), 5.18 (dm, J = 17.6, 4H, NCH2CH=CH2), 5.22 (d, J = 1.2,2H, C=CH2), 5.20–5.25 (m, 4H, NCH2CH=CH2), 5.75–5.95 (m, 4H,NCH2CH=CH2). 13C NMR (CDCl3) �: 30.5 (2 × OCH2CH2S), 30.5 (4 ×OCH2CH2S), 35.7 (4 × SCH2C=), 37.2 (2 × SCH2C=), 41.0 (2 × CH2SC=S),53.5 and 56.5 (2 × brs, 4 × NCH2CH=CH2), 70.3 (4 × CH2O), 70.3 (2 ×CH2O), 115.9 (2 × =CH2), 117.2 (2 × =CH2), 118.5 (4 × NCH2CH=CH2),130.2 and 131.1 (2 × brs, 4 × NCH2CH=CH2), 139.5 (2 × C=CH2), 140.8(2 × C=CH2), 197.5 (2 × C=S). HRMS (ESI) [M+Na]+ calcd. for [C42H68

N2O3NaS10]+: 991.2329; found: 991.2313. FT-IR (neat) � = 3078 (w),2945 (w), 2910 (m), 2859 (m), 1638 (w), 1466 (m), 1397 (s), 1350 (w),1298 (w), 1225 (s), 1171 (w), 1097 (vs), 992 (m), 906 (vs), 731 (m),663 (w), 551 (m) cm−1.

(2,15,28,41-Tetramethylene-7,10,20,23,33,36-hexaoxa-4,13,17,26,30,39-hexathiadotetracontane-1,42-diyl)bis(diallylcarbamodithioate) (11g)

Yield: 72%. Compound slowly crystallised from a concentratedsolution in dichloromethane at 0 °C. mp: 38 – 43 °C. 1H NMR(CDCl3) �: 2.59 (t, J = 6.8, 8H, OCH2CH2S), 2.61 (t, J = 6.8 Hz, 4H,OCH2CH2S), 3.24 (d, J = 0.8, 4H, SCH2C=), 3.29 (s, 8H, SCH2C=), 3.58(s, 12H, CH2O), 3.59 (t, J = 6.8, 8H, OCH2CH2S), 3.60 (t, J = 6.8, 4H,OCH2CH2S), 4.14 (d, J = 1.2, 4H, S=CSCH2C=), 4.31 and 4.62 (2 ×br-s, 8H, NCH2CH=CH2), 4.98 (s, 4H, C=CH2), 5.06 (d, J = 1.2, 2H,C=CH2), 5.17 (dm, J = 17.6, 4H, NCH2CH=CH2), 5.21 (d, J = 1.2,2H, C=CH2), 5.23–5.28 (m, 4H, NCH2CH=CH2), 5.7–5.9 (m, 4H,NCH2CH=CH2). 13C NMR (CDCl3) �: 30.3 (2 × OCH2CH2S), 30.3 (4 ×OCH2CH2S), 35.6 (4 × SCH2C=), 37.2 (2 × SCH2C=), 41.0 (2 ×CH2SC=S), 53.5 and 56.5 (2 × br, 4 × NCH2CH=CH2), 70.2 (6 × CH2O),70.6 (4 × CH2O), 70.6 (2 × CH2O), 115.9 (2 × =CH2), 117.1 (2 × =CH2),

118.4 (brs, 4 × NCH2CH=CH2), 130.4 and 131.0 (2 × brs, 4 ×NCH2CH=CH2), 139.5 (2 × C=CH2), 140.8 (2 × C=CH2), 197.4 (2 × C=S).HRMS (ESI) [M+Na]+ calcd. for [C48H80N2O6NaS10]+: 1123.3116;found: 1123.3115. FT-IR (neat) � = 3078 (w), 2945 (w), 2910 (m),2859 (m), 1638 (w), 1466 (m), 1397 (s), 1350 (w), 1298 (w), 1225 (s),1171 (w), 1097 (vs), 992 (m), 906 (vs), 731 (m), 663 (w), 551 (m) cm−1.

(2,2=-(2-Methylenepropane-1,3-diyl)bis(sulfanediyl)bis(methylene)bis[prop-2-ene-2,1-diyl]) bis(diallylcarbamodithioate) (11h)

Yield: 87%. 1H NMR (CDCl3) �: 3.13 (d, J = 1.2, 4H, SCH2C=), 3.21 (s,4H, SCH2C=), 4.15 (d, J = 1.2, 4H, S=CSCH2C=), 4.33 and 4.64 (2 ×br-s, 8H, NCH2CH=CH2), 4.98 (s, 2H, C=CH2), 5.06 (d, J = 1.2, 2H,C=CH2), 5.19 (dm, J = 17.2, 4H, NCH2CH=CH2), 5.24 (d, J = 1.2, 2H,C=CH2), 5.2–5.3 (m, 4H, NCH2CH=CH2), 5.8–5.9 (m, 4H, NCH2CH=CH2).13C NMR (CDCl3) �: 34.8 (2 × SCH2C=), 35.9 (2 × SCH2C=), 41.4 (2 ×CH2SC=S), 53.6 and 56.6 (2 × br, 4 × NCH2CH=CH2), 116.1 (=CH2),117.2 (2 × =CH2), 118.5 (2 × brs, 4 × NCH2CH=CH2), 130.5 and 131.1 (2 ×brs, 4 × NCH2CH=CH2), 139.5 (2 × C=CH2), 140.4 (C=CH2), 197.5 (2 ×C=S). HRMS (ESI) [M+Na]+ calcd. for [C26H38N2S6Na]+: 593.1257;found: 593.1256. FT-IR (neat) � = 3078 (w), 2980 (w), 2910 (m),1637 (m), 1464 (s), 1395 (vs), 1335 (m), 1266 (m), 1223 (vs), 1169 (s),1125 (w), 1098 (w), 991 (m), 965 (w), 901 (vs), 742 (m), 697 (m) cm−1.

(2,6,10,14,18-Pentamethylene-4,8,12,16-tetrathianonadecane-1,19-diyl) bis(diallylcarbamodithioate) (11i)

Yield: 93%. Compound solidified very slowly at 5 °C. 1H NMR(CDCl3) �: 3.10 (s, 4H, SCH2C=), 3.15 (s, 8H, SCH2C=), 3.17 (s, 4H,SCH2C=), 4.11 (s, 4H, S=CSCH2C=), 4.29 and 4.60 (2 × br-s, 8H,NCH2CH=CH2), 4.95 and 4.96 (2 × s, 6H, C=CH2), 5.02 (d, J = 0.8,2H, C=CH2), 5.15 (dm, J = 17.2, 4H, NCH2CH=CH2), 5.20 (d, J = 0.8,2H, C=CH2), 5.2–5.3 (m, 4H, NCH2CH=CH2), 5.7–5.9 (m, 4H, NCH2

CH=CH2). 13C NMR (CDCl3) �: 34.6 (6 × SCH2C=), 35.7 (2 × SCH2C=),41.2 (2 × CH2SC=S), 53.4 and 56.4 (4 × NCH2CH=CH2), 115.8 (=CH2),115.9 (2 × =CH2), 117.0 (2 × =CH2), 118.3 (4 × NCH2CH=CH2), 130.3and 130.8 (4 × NCH2CH=CH2), 139.2 (2 × C=CH2), 140.2 (2 × C=CH2),140.3 (C=CH2), 197.2 (2 × C=S). HRMS (ESI) [M+Na]+ calcd. for[C34H50N2NaS8]+: 765.1632; found: 765.1623. FT-IR (neat) � =3076 (m), 2907 (m), 1638 (m), 1465 (s), 1397 (vs), 1335 (w), 1275 (m),1223 (vs), 1169 (w), 1125 (m), 1098 (m), 992 (m), 903 (vs), 875 (m), 746 (s),665 (m), 551 (m) cm−1.

Methylene bis(diallylcarbamodithioate) (13)Unoptimised yield: 63%. 1H NMR (CDCl3) �: 4.27 and 4.60 (2 ×

br-s, 8H, NCH2CH=CH2), 5.19 (d, J = 17.4, 4H, NCH2CH=CH2), 5.24 (d,J = 14, 4H, NCH2CH=CH2), 5.38 (s, 2H, SCH2S), 5.7–5.9 (br-s, 4H,NCH2CH=CH2). 13C NMR (CDCl3) �: 46.5 (SCH2S), 53.7 and 56.8 (4 ×NCH2), 118.6 and 118.9 (4 × CH=CH2), 130.2 and 130.9 (4 × CH=CH2),197.0 (2 × C=S). m/z (EI) 358 (<0.5%, M+), 218 (100%), 172 (12%),140 (22%), 98 (7%), 73 (14%). HRMS calcd. for [C15H22N2

32S4]+: 358.0660;found: 358.0664. FT-IR (neat) � = 3079 (w), 2980 (w), 2910 (w), 1640 (m),1466 (s), 1430 (m), 1396 (vs), 1334 (m), 1274 (w), 1226 (vs), 1166 (s),1124 (m), 966 (m), 921 (vs), 768 (m), 736 (m) 640 (m), 550 (m) cm−1.

Supplementary material1H NMR, 13C NMR, IR, and MS data of all new compounds are

available with the article through the journal Web site at http://nrcresearchpress.com/doi/suppl/10.1139/cjc-2013-0426.

AcknowledgementsThe authors wish to acknowledge the support of ARC DP0877382

in this work and would like to thank Drs. Tara Schiller, DanielKeddie, and San Thang for reading the manuscript and (or) helpfuldiscussions.

References(1) It should be noted that there is no relationship between the term “photo-

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