Synthesis and X-ray structural study of 1-adamantylmethyl 2-cyanoacrylate and 1,10-decanediol bis-2-cyanoacrylate

2l72 Russian Chemical Bulletin, Vol. 45, No. 9, September, I996 Synthesis and X-ray structural study of 1-adamantylmethyl 2-cyanoacrylate and 1,10-decanediol his-2-cyanoacrylate V. N. Kltrustalev,* 0. V. Shisltkin, S. V. Lindemau, Yu. T. Srruchkov,’ M. A. Galkina, and Yu. G. Golalobav A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 ul. Vavilava, 117813 Moscow, Russian Federation. Fax: 007 (095) I35 5085 l«Adamantylmethyl 2~cyanoacrylate (1) was prepared by the reaction of 2-cyanoacryloyl chloride with l—adamantylmethanol. l,l0-Decancdiol bis-2—cyanoacrylate (2) was synthe- sized by transesterification of methyl 2-cyanoacrylate with l,lO-decanediol. Esters 1 and 2 were studied by X-ray structural analysis. Key words: 2-cyanoacryloyl chloride; methyl 2—eyanoacry|ate, transesterification; I-adamantylmethyl 2-cyanoacrylate, l,I0—decanediol bis-2-cyanoacrylate. X—ray structural study. Esters of 2—cyanoacrylic acid have been known for more than 45 years.‘ These esters are widely used in polymer chemistry as a basis for quick-acting single- component cold-setting adhesives.’ Recently, 2~cyano— acrylates have found use in laboratory practice as highly active reagents for organic synthesis.“ With the aim of obtaining quantitative characteristics relating the reactivities of 2-cyanoacrylates to their struc- tures, we carried out an X-ray structural analysis of compounds of this class. In this work, we report on the synthesis and discuss the results of X-ray structural analysis of Ladamantylmethyl 2~cyanoacrylate (1) and 1,10-decanediol bis—2—cyanoacrylate (2). Compound 1 was prepared by the reaction of 2-cyanoacryloyl chloride with I-adamantylmethanol in analogy to the procedure described previously5v‘ (Scheme 1). Scheme 1 O o I l H2C:(EéC| + 1-AdCH2OH -:0-,> H2c=ccocH2Ad—1 c c N N Ill lll Ester 1 is a crystalline colorless compound. The ‘H NMR spectrum ofthis compound is typical of esters of 2-cyanoacrylic acid. l,lO- Decanediol bis-2-cyanoacry- 1 *1 Deceased in I995. late 2 was synthesized by transesterification of methyl 2-cyanoacrylate with l,l0—decanecliol in the presence of p-toluenesulfonic acid7 according to Scheme 2. Scheme 2 ‘I? p-MeC H 80 OH 2 H2c=ccoMe + HO(CH2)mOH —————._%:—c3—1———» CEN ll —'> H2C=(FCOC5Hw- CEN 2 A multistage synthesis of bis-2-cyanoacrylate 2 has been reported previously.‘ The properties of the com- pound obtained (m.p., ‘H NMR spectrum) correspond to the data in the literature.“ The X—ray structural study demonstrated that mole- cules 1 and 2 have geometries typical of esters of acrylic acid (Tables l—~4).9 However, the methylene H atoms show a pronounced acid character, apparently because of the presence of strong electromwithdrawing groups (cyano and ester groups). This accounts for the short intermolecular contacts typical of weak hydrogen bonds that are observed in the crystals of compounds 1 and 2 (Figs. l and 2): C—H'~O=C for compound I [O(l ') (x, y — 1. z)'"C(3). 3.49(1) /5»; 0(l ') (X. y — 1. z)'“H(3A). 2.4(l) A; O(l ')-~H(3A)—C(3), l.67(6)° and O(l)~-C(3‘), 3.43(l)A; O(l ')-~H(3E), 2.4(l)A; O(l ')~vH(3E)——C(3'). l68(6)° for two crystallographically independent mol- ecules l and ll, respectivelyI§ C~H~‘N=C for com- Translated from Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2288—2292, September. 1996. l066-5285/96/4509-2 l 72 © I997 Plenum Publishing Corporation Synthesis and X-ray structural study of cyanoacrylates Table I. Bond lengths (d) in the structure of I Bond d/A Bond d/A Molecule 1 Molecule 11 O(1)—C(1) 1.19(1) O(1')—C(1') 1.19(1) O(2)—C(|) 1.34(1) O(2')—C(l') 1.34(1) O(2)—-C(4) l.48(l) O(2')—C(4') l.46(1) N(1)—C(5) 1.14(1) N(1’)——C(5') 1.l2(1) C(1)——C(2) 1.49(l) C(1')—C(2') 1.47(l) C(2)-C(3) 1.28(1) C(2')—C(3') 1.112(1) C(2)——C(5) 1.45(1) C(2')—C(5') 1.45(1) C(4)—C(1A) 1.S1(1) C(4')—C(lB) 1.53(1) C(1A)—C(2A) 1.511(1) C(lB)—C(2B) 1.54(1) C(1A)—-C(8A) 1.53(1) C(13)-C(88) l.S4(1) C(lA)—C(9A) 1.56(1) C(1B)—C(9B) 1.54(l) C(2A)—C(3A) 1.56(l) C(2B)—C(3B) 1.49(1) C(3A)-—-C(4A) 1.52(1) C(3B)——C(4B) 1.54(1) C(3A)—-C(10A) l.49(1) C(3B)-—C(l0B) 1.54(1) C(4A)—C(5A) 1.54(1) C(4B)——-C(SB) 1.52(1) C(5A)-C(6A) 1 1.52(l) C(58)-—C(6B) 1.S3(1) C(5A)—C(9A) 1.511(1) C(5B)—C(9B) 1.50(1) C(6A)—C(7A) 1.51(1) C(6B)—C(7B) l.53(1) C(7A)—C(8A) l.54(1) C(7B)——C(8B) 1.53(l) C(7A)—-C(10A) 1.55(1) C(7B)——C(10B) 1.53(1) pound 2 [N(1) (1 + x, 1 + y, z)~‘C(l), 3.380(3) A; N(1) (1 +x. 1 +y. z)'"H(1A). 2-59(2) A; N(1)'"H(1A)-C(1). Russ.CI1em.BuII., Vol. 45, No. 9, Septembei, I996 2173 l38(l)° and N(1) (-1 - x. 2 ~ y, 1 — z)~-C(l). 3.477(3) A; N(1) (4-I - x, 2 — y, 1 - z)-~H(1B), 257(2) A; N(1)—~H(1B)—C(l), 160(l)°|. Under the re- action conditions, these interactions may, apparently, promote the initial coordination of nucleophilic reagents in the vicinity of the reactive groups (coordination of proton—acceptor nucleophiles to the methylene H atoms through hydrogen bonds). Note that the analogous es- ters of acrylic acid can also form weak C—H...X hydro- gen bonds;'°"‘” however, it is difficult to estimate the relative acidities of methylene H atoms in derivatives of acrylic and cyanoacrylic acids based on structural data alone. Evidently, the cyano group additionally increases the acidity of the protons of the =CH2 group and thereby enhances the reactivities of compounds 1 and 2. However, this suggestion calls for more detailed analy- sis, which we plan to carry out in the future. Experimental The ‘H NMR spectra were recorded on a Bruker WP-200SY instrument (200.13 MHz) in C6D,-, relative to S1MC4. 1-Adamantylmethyl 2-cyanoacrylate (l). A solution of 1—adamanty1methanol (1.66 g, 0.01 mol) in toluene (10 mL) was added to a solution of 2—cyanoacryloy1 chloride prepared Table 2. Bond angles (0)) in the structure of 1 Angle mldeg Molecule 1 C(1)-—O(2)—C(4) 119.8(6) O( 1 )—C( 1)-—O(2) 125.2(8) O(1)—C(1)—C(2) 124.1(7) O(2)——C(1)-—C(2) 110.6(7) C(1)—C(2)—C(3) 124.6(7) C(1)—C(2)-C(5) 114.6(8) C(3)——C(2)—-C(S) 120.6(9) O(2)—C(4)—C(1A) 110.0(6) N(1)-C(5)—-C(2) 177.2(9) C(4)—C(1A)—-C(2A) 112.1(6) C(4)—C(1A)—-C(8A) 110.3(6) C(2A)—C(1A)-—C(8A) 110.2(6) C(4)—C(lA)-—C(9A) 106.2(6) C(2A)—C(1A)—-C(9A) 109.0(6) C(8A)—C(1A)--C(9A) 108.9(6) C(lA)—C(2A)—C(3A) 109.7(6) C(2A)—C(3A)—C(4A) 109.0(7) C(2A)—C(3A)—C( 10A) 109.1(7) C(4A)—C(3A)—C(10A) 110.1(6) C(3A)-C(4A)—C(5A) 108.8(7) C(4A)——-C(5A)——C(6A) 108.9(7) C(4A)—C(5A)-—-C(9A) 111.0(7) C(6A)—C(5A)-—C(9A) 110.9(6) C(5A)-C(6A)—C(7A) 108.8(6) C(6A)—-C(7A)~—C(8A) 110.1(7) C(6A)-~C(7A)~—C( 10A) 110.1(7) C(8A)—C(7A)—C( 10A) 108.3(6) C(1A)—C(8A)—C(7A) 109.1(6) C(1A)-C(9A)—C(5A) 108.0(6) C(3A)——C(10A)-C(7A) 110.2(7) Angle to/deg Molecule [1 c(1')—o(2')—c(4') 118.5(5) o(1')-c(1')—o(2') 124.0(8) o(1')—c(1')—c(2') 124.4(8) o(2')—c(1')——c(2') 111.5(7) c(1')—c(2')—c(3') 125.1(8) c(1')-—c(2')—c(s')‘ 115.5(8) c(3 ')—-c(2')—c(5') 119.5(9) o(2‘)—c(4')-—c(113) 107.5(5) N(l ')——c(5')—c(2') 177.9(9) C(4 ')—c(1a)—c(2 111.5(5) C(4’)—C(1B)—C(8B) 113.1(5) C(2B)—C(1B)—C(8B) 108.1(6) c(4')—c(113)——c(9a) , 109.0(5) c(213)—c(111)-—c(913) 107.4(5) C(8B)—C(1B)--C(9B) 107.5(5) C(lB)—C(2B)—~C(3B) 112.2(7) C(2B)——C(3B)—C(4B) 108.0(7) c(213)—c(313)—c(1013) 110.4(7) C(4B)——C(3B)—C(l0B) 109.0(7) C(3B)—C(4B)-C(53) 109.3(7) C(4B)—C(5B)—C(6B) 109.4(8) C(4B)—C(5B)—C(9B) 110.5(8) c(513)—-c(513)——c(913) 109.1(7) C(5B)—C(6B)-C(7B) 110.4(7) C(6B)-—C(7B)—C(8B) 107.9(7) C(6B)-—C(7B)—C(10B) 108.7(7) C(8B)—C(7B)~—C(10B) 109.4(7) C(1B)~C(8B)—C(7B) 111.8(6) C(1B)——C(9B)-—C(5B) 111.1171 C(3B)—C(10B')——C(7B) 109.9(7) 2l74 Rus5.Chem.BuIl., Vol. 45, No. 9, September, I996 Khrustalcv er al_ Table 3. Bond lengths (d) in the structure of 2 Table 4. Bond angles (03) in the structure of 2 Bond d/A Bond d/A Angle cu/deg Angle cu/deg 0(1)-c(1) 1.202(3) c(2)—c(4) 1.442(3) CU)-0