Synthesis and Gelation Properties of N,N'-Bis(3,4,5-trialkoxy)benzoylurea: Terpene and Perfume Gels

I 250 Chemistry Letters Vol.34, No.9 (2005) Synthesis and Gelation Properties of N,N’-Bis(3,4,5-triaIltoxy)benzoyltirea: Terpene and Perfume Gels Kallji Kuhn‘ and Akii-a Mort‘ Schuul (1fDrItLi:Iry. Heallh St'ience.t University offlakkaida. I757 Kllllllijlwll. Ixlllktlri-Tnbelvll. Hokkaido 06/-0293 llniiiiiiie fur Mam-inlr Cltelilixtijv and Ellgilleerirtg, Kyirriin urriirerriiir. Kn.rrrgn.Irnrn, Kusugzl, Fukuoka XI6-X580 (Received June 2|. 2005: CL—050793l New nrganogelatnr, NM- st? 4,5-tridodecyloxy)benzoyl- men (I). gelled organic liquid such £I.\ alcohol. hydrocuboiis. ethyl acetate. salad oil, terpcnes. and essential and perfume oil at low concentration of gelator. The ierpene and perfume gels show good release of the volatile components for a long time Organogels tire of great significance particularly let their potential application to template for materials synthesis. drug dc» livery, separations, cosntetic~. sensors. and The number of organogelators has rapidly increased UVCT I5 years. In the putt. new organogelatcirs often have been discov- ered accidentally and their studies have been dedicated to under standing the relation between the structure of gelutors and gclat» ion behaviors’. The aggregation of orgnnogetntrrrs into libttius networks is driven by multiple, weak ililemclitms such as di- pole—dtpole. van dcr Waals, hydrogen-bonding. and It-stat-king interactions. Gelntors are generally elassilied by their driving force for molecular aggregations into two categories of ni:rii-hy- drogcn bond-heseti and hydrogen liontl—lau.sed gelatursfi Amide compounds. such tlh timinri acid3 and urea.‘ hydroxyl compounds such as I2-hydroxystearic acid (I2-HOSA)5 and sugers° belong to hydrogen bond—laascd geltitors. While cho|estem|.7 anthra- cene.“ and tropone denvatives"-'" belong to non-hydrogen bond-based gelatois. Recently. we have reported a new organe- gelator” with it bitropone core and two 3.4.5»ti1‘dndccy-Ioxyben- zoylamino groups. The hitmi-ione derivative (BTP) gelled organ‘ it; liquids such an Itttlg-Chitin alcohol. hydoroczirbon. ethyl acc- niie, nnd citmnellnl and its aggregntitrn is driven by 7|’-slacking interactions between intermncciilai bitropnne rings. Based on the results of critical gelation concentration (CGC). BTP gelled l-decantil selectively. However, BTP cannot be used in low con- centration. In this paper. we report the synthesis rind gelatinn properties at N.lV'»|)is(3.4,5-tridodecyloxy)bcnznylui*eti (1) ii: :i new organogeliator and its application to terpcne and perfume gcls (Scheme 1). Reaction of uteu with 3.4.5»tridodecyloxybcnzoyl chloride cirnreu Cizflzsomf D °“""° uric 00 O NH OCHH” 0 ET? CCtgH25 0Ci2*‘2s O 0 0 912N250 N1" \ °‘3i2N:5 If» n l, Ciztlzro OCi2H2s °Ci2"‘n 0CtzH2s 1 Scheme I. in a DMAP—pyndine solution afforded the diamide derivative 1. The structure of 1 was identified by ‘H NMR. mass spectros- copy, and elemental analysis.“ The gclation abilities of L BTP. zind I2-HOSA for a range oforganic Solvent war; etniiiineu by dissolving approximately 1— l00mg of compound in I mL of the desired xolvent under heat‘ ing The solubility of these compounds at room remparature is very poor in most solvents. Upon cooling to 25 C, a gel, a prt:~ cipitiite or Cl clear solution was observed, depending on the sol- vent. Interestingly. compound I gelled organic solvents such as ethyl acetate. alchohols (C4-Clll). hydrocarbons (C6436). tetraliydrofuran. and salad oil. The photograph ol’ l—l-dccunol and l—ethyl acetate gels are shown in Figure in. Figure lb shows Figure 1. Photographs of (a) I-1-decanol gel (left. l.0tiig/ lmL). lathyl acetate gel trigltt. l0mg/mL) and (la) optical micrograph of l—ethyl tieeuiie gel (l0mg/I mL). Table 1. Minimum gel concentrations (MGC. gL") of I. BTP. and I2-HOSA at 25 C 12-HOSA I2-HOSA Solvents i BTP mm“ (99%) siilad Oil 1.9 7.4 2i 2.2 n»Hexane 8.4 Sol“ 30 6 5 ii-Decline 3.5 70 20 2.8 it~HcxadeI.-an: 3 3 9.1 8.6 1.9 Methanol Crysr‘ tristir‘ Sol” Sol“ Ethanol Cry.~t' lnsul“ Sol” sol“ l—Pmp:inol :0 lnsol‘ sot“ Sol” I-Bulznnl 2 5 lnaol“ Sol” Sol” t-Hexariol l l6.5 still‘ still t-oetniiol l 9.8 Sol" 95 l~Decanol l 55 still’ 90 Elhylacetute 3.3 l|.5 Sol” 45 THF 25.7 Sol” Sol” strl" DMF Sol” soil’ Sol” Sol” 'Cryst: Crystallization. ES olution. “lnsol: lnsoluhle.7 Copyright © 2005 The Chemical Society of Japan Chemistry Letters Vol.34, No.9 (2005) an optical micrograph of the gel phase or l—ethyl acetate (5.0 wt%) taken at 25 C on cooling from an isotropic liquid state. Highly iinertwlncti. rod-like fitter», were observed in a network structure. The fibers it ith diameters ofca. l um align to form nct— work structures. The XRD pattem for xerogel of I (prepared from l—ethyl acetate gel) display a single brand reflection peak in d = 2.9 nm in the small—angle region and one broad reflection in wide rilnge region at (I: 0.4 nm. However. it is unclear whether the broad blind in wide-range region is based on tlte coexistence of different mesoniorpliic organitatitins or slightly disordered structure oi’ the organogel.” The layer spacing (d) is shorter than the extended molecular length (4.4 rim) of 1. sug- gusting that it forms 3 tilted layer or interdigitaled structure. Minimum gel concentrations (MGC. g L") of I. BTP. and 12-HOSA (80% from Tokyo Kasei and 99% fmm Aldrich) for vario ~ olvents are detenuined as shown in Table l. The gelat- ioi:i abi y of 1 is better than that of BTP. Compound I is a good organogelator for long chain alcohol. That is. I has it long chain alcohol gelation selectively. While I2-HOSA has long chain hy- drocarbon gelatlon. The MGC value of l. BTP. and 12-HOSA decrease with increasing of carbon number in hydrocabon and itlcohol. The geltttitm ability of I for alcohol is superior to that or 12-IIOSA. while that of 1 for hydrocarbon is infenor to that of I2-HOSA This suggest that the solvent alcohol inhihit intermolecular hydrogen bonding between hydroxyl group and carboxylic acid ul’ I2-HOSA. As an application to new materials ol organogelator l. ter- pene and perfume gels were prepared. In perfume, fragrance and deodront goods. water-soluble gelators such as cal1'a_gheen- an. agar. collagen. gellan gum. and gelatin. etc. have been used for the gelatiuiis of water-conta ing terpenes. essential oils. and perfumes. So. the purity ofthe oils in the gel: is low and most of components of these goods are water. Fonunately, under the conditions at‘ gelaz-rgctnic liquid (I Snlg/I nlL). compound I could gel the terpenoids and essential oils such Iinalool. geraniol. nerol. citronellol. at-tcrpineol. nerolidol, liinonene, myrccnc. /3—pinene. 3-earene. terp' crle. squalene. linallyl acetate. neryl acetate. citronellal. rose oil. lavender oil. bergamut oil. Japanese mint oil. terpentin oil. orange oil. and lemon oil. etc. (Figure 2). Under similar condition. 12-HOSA could gel the terpcne hyi.1ro— cabons such as myrcene fl-pinene. 3-carcne. terpinene. limo» nene. squalene, and cssnti oils containing much amount ol’ lerpene hydroctibons such as orange oil and lemon oil. but could not get the terpcne alcohols. The release tests of the volatile colnponenth from l—terpene and perfume gels were employed. The caps of the glass tubes Figure 2. Gels (5 mg/l mLl of l—cttmne|lol. l—rose oil, I—lav- ender oil. I2-HOSA—limonene, I2-HOSA—0range oil. and I2- HOSA—|emon oil. 125] Table 2. Weight Changes (mg) uflhc perfnfllc gels containing I and ne-.it liquids by the release te- s of the volatile components _ I _ l Weight Weight (III ) Solvents/Status /mg /mg arm 324‘? Linallnl/Gel 1.865 595.3 469.3 Linallcl/Liquid 0 590.0 442.| Rose oil/Gel LR63 607.0 569.2 Rust‘ uil/Liquid 0 597.5 558.] Lavender oil/Gel 1.969 67(l.| 607.2 Lavender oil/Liquid 0 658.3 565.8 Bergamot oil/Gel |.9I9 596.9 479.9 Berganlol oil/Liquid 0 568.6 309.9 containing the fragrance gel and neat liquid were opened. they were left at IlIOl'I1I¢IlI|1¢l’fll|II’€.tll|dIiIC weight changes at lhe gels and neat liquids were investigated. as shown in Table 2. The weights or the gels and neat liquids were decrea~ing with time. The weight-decreasing rates of the gels were slower than those of neat liqui . suggesting that the gel state controlled the release of the volatile components. After 324d. each gel was keeping the gel state and had it characteristic scent til‘ the terpene and perfume. In conclusion. compound I had good gelatitin ability for terpenes and essential oils. We succeeded in preparation of the perfume gels containing 99.5% or more of terpenes and essential oil for the first time. The ierpene and perfume gels showed good release oi the volatile components rora long time. Their gels will be utilized as fragrance and deodorant agents. References and Notes I ‘Gels Hiiiitllstiok.“ ed. by Y. osatlii and K. Kajiwura. NTS Cm. Japan (I997): K. Hanatiiisa. Mimi Zlilfydl, 4. s t2tlo4). 2 P. Terech and R. G. Weiss. Clmn. lien. 97. 3 L13 (I997): K. ltiiiiatnisa and H. Slllral. Hyfllllr/1.36. 291 (I998) .van Bali and B. L. Feringit. . 7 372000):t:l.Groriwattliiritls.sliink .Grnnwald.E.Srlip.:tlidS.Shinkai. Curr. opiii. Calloiil Iiimfnre ri.. 1. I48 tztm); N. w. Fottnsvis and A Desllpande. Curl‘. Org. Climi. 5. 39.1 tztm). 3 M. siiztitti, Y. Niitajinia. M. viirnon». M. Kininri. H shit-ai, and K. Hannbusu Org. Blrlmtll. cIimi.. 2. I lss tznodl. 4 K Hanaliusa. K. slnrniira. K Htrose. M Kiinnrn. and H Shir client. Lu: I906. RES. 0. Wang iinil A. D. Hlllltliltm. climi. Cu iniiii.. 200 .Jlo. 5 Y. Tiiniguclii nntl K. Suzuki. 1. P/lV.\'. climi.. 7:. 759 tum): T. rninni-a. stiitizui Kiiilmirlii. 72. 25 (H199). ti K Yozll. Y. Ono. K. Y0§llll‘lliII"tL Y. ono. T Alma. H. slnninori. M Talreiictii. s. siiinit.-ii. and D N Rtlnhfllldl. chm. comintiit. I9‘18.9tJ7. 7 wt; Ai.-rec andG L. Bertrand. Niiiim-. 19. 45(Itl977 - s. Kawnnti. and s. Shitlkni. mi. (‘iiiiu IL. 2003. I. K. Kiitxi. .1. 0lcuSt' 53. 467 (2004). . R. Utemiolllen. F, Fttges. H. B0|laS~La|IR'.III. and J.-P Desverlyn. 1. clmii. Srrt:.. climi. cnminiin. l99l. -H6. a M. Hflthilllulu. s uitie. and A. Mon. 44-: Mritcn. is. 797 (21103)-. K. Kubo. Kugrikii. 59. 56 (2004). in K. Kuho. A. Mori.alidS tiiitc.c.'rtcliieisite.J alerisr-i'..5:. 575 (2004). ll spectral data oi I: 'HNMR t-000MHz. rlxlii 8 tutti (IEH. J =70Hzl. t.2mi.52 tloall. in). L75 (4H. quint. =ti.6H . L8-t (SH. qinni. J : 5.5 Hz). 4.tl5 «H. i. J : 5 bl-I1]. 4 no tall I = ri.(iH1l. 7.14 (alt. sl. FAB Ms: m/.' I374 (M + H) Found’ C. 75 93 H. ll.38. N. 1.99%. Calcd loi Cml-l.,.,N;0.: C, 76.04; H. I l.-$4: N. 2.l14%. I2 ‘Membranes and Molecular Asseniblles: The Synkinetic Appmaicli." ed. by J H. Fiitiriiop and J. Knening. The Royal Society oicneiniury (I994). p I85. Published on the web (Advance View) August 6. 2005; DO] l0.|246/c|.2005.l250