B16 RIM Pw PER Vol. 16, No. 3 1996 & 9.8 — JOURNAL OF CHINESE SOCIETY FOR CORROSION AND PROTECTION —_ Sept, 1996 SIRATEMRCADH FB Seth te ae KR FRE WR RKE MAM RRA RRR KML (ARKFRPR, RAF AR RR 430072) WE RATER HL A AEF IER ED, ET 20 HE J MNDO #1 CNDO/2 72k Ge Hit HEH 5} FO LAS, LIP, I MR SAE He. Sh AE Ak RG oA AT PO ASHE COP He T SAL OM Me ICA Ey. SER, wh aa ARRAN CRNA, FSET TARE RA, RTE Bit SAF ST BIT MAA RG 2 AL SY A AB) OO ATE REE TEU Be SCAT A i 0 OE A EZ DK RP RT a FA MNDO Fx RAGit SE TRE RIAA LA, EE, RT ET i ea SSC HP E75 A A Ek A 2 EE A SPE ATT TE 1 SBS 11 Sie EHR RICE, CTE MRE RMR. RMR, BRR SERS P. 12 RBAK RAB HEE 1 IG PARE AE (icone). (BEDE FPN HCI Al NaCl Be pH=2 SRL, PRR CI- FF BUE A LSmoldin™® , 9¢ ph FH CE 5} He 0.1%, BRAT TA] 53h HH ADP ACT HE 20 (O.2wt%C) HEE BS TH, SRT TRIE TEMG @ A. BORER SHR, eR OP Ae eT 1995-03-30 fc 1995-09-01 ic FI AC196 HC(4) — Nia) ll i} No(s) (2H \ 7 Nay H ee uM) HC(a) — NOs) I ie HC(5)— C(2)R--C(6)Hs N\ Na) H 2 aeRO (2) MeIM) H3C(6) —- C(4) -~ N(3) 4 ll HC(s) —C(2)H N 7 nq) H 4 Poke (4- MeIM) Hy C(6) ~ C(4) — N(3) t q HCi7) - C(5} — C(2)H t \ 7 HO(s) Na) H 4- FE 5 Bokeh ({MHXIM) 13° LEAR SP LG ak 5 By PO He 16 HsC -C(4) - -Ni3) fi N HC(s) | C(2)H + Zu \/ \ xo) ers ? (4 -MelM2u) HO(5) == Ci4)H ' \ HN(1) N(3)H \/ C{2) i. mea = 2 ° (IMDN - 2) CH HyC + C(4) == C(3) — N < ! ' (CHaSO,Na Hs N(5) C(2) = 0 \ 74 N{1) Rone (ANG) cH, HsC — C(4) = C(3) —N I \ Hs H3C — N(5) C2) = 0 \/ N(1) mae (APR) AR HEPA EA (9 BE BS IE cone MUAH 0 WF HEL. 2 BFkSuR Fa TD Dk a Be A A OH HE RE, FA] MINDDO Fy BA KE, 2- FARGO 4 FE3m POM: SAARI i hE a HE REX 197 WRG. 4 BRAG 5 FB HAR me AK Ae A 2 OH IL fa BE Am GHEE (Enomo) AUB 2 Wi MER (ELumo) » N(1). N(3), NG) AFM ORE TOR LAAT HY ZA Oring WTR 2. WASATCH A RIT PG SHR FA TTR TT 3 ‘Table 1 Inhibition efficiency of the tested compounds Compound (uA/m?-10*) (%) ™M 13.5 87.7 2-MeIM 18.3 83.4 4-MeIM 11.6 89.5 MHXIM 28.2 744 4-MeIMZn 14.0 87.3 IMDN-2 30.3, 72.5 ANG 27.7 4.8 APR 37.9 65.5 Blank 109.7 Table 2 Energy of the HOMO and LUMO and net charge calculated by MNDO- Compound Enomo. Euumo. Net Charge (1.6021x10~'C) ev. eV Qn Quesy Qring IM 9.0440 0.9540 0.2416 -0.2373, 0.5522 2-MeIM 9.1901 0.9164 0.2411 0.2317 0.5454 4-MeIM 8.9960 0.8572 0.2464 = 0.2206 0.5519 MHXIM 8.6324 0.3602 0.1104 0.1603 0.5150 IMDN-2 “8.7878 0.7706 «= 0.3523 0.3039 0.2618 ANG" 0.0305 -0.1070—-0.0763(Quis)) (0.1875 APR* 0.1148 0.1313 -0,0902(Qyi¢5))__(0.1367 * with CNDO/2 Table 3 Contribution of P, orbital of the Atoms of Five-membered ring to the frontal orbital Atom IM 2-MeIM 4-MeIM MHXIM, Number HOMO LUMO HOMO LUMO HOMO LUMO HOMO LUMO N(1) -0.1865 0.4268 0.1568 -0.4260 0.1848 0.4197 0.1504 0.4749 CQ) -0.5097 0.5128 0.5229 0.5640 0.4801 0.4874 0.5791 ~0.4368 N(3) -0.1358 0.1840 0.2117 -0.2745 0.1233 -0.1528 0.0678 0.0415 C(4) 0.5582 0.3858 -0.5084 -0.2992 0.5477 -0.4048 0.5022 0.3678 C(5) 0.6119 0.6084 -0.6123 0.5545 0.6113 0.6208 0.5546 _-0.6250198 EGS BP 16 & PRS REAR, ASEH MNDO Jy Pe RAL SE A LAY, aH] CNDO/2 WK HET. SMKER EAM HSM (GC, BAF) 31 AAR S). RRMA Fi Exomo . Expmo MN(1). N(5) Hc Hp Hh Hy By tH] FH 2, 3 Hit 3.1 PRB SERRE A TEA SRR OK Ok CAG Ae 8 BR KAR HEHE 2 PR BE SM NCL) BR FRB Ong) SRL PALS RMS, Ae 11 = 63.8203 ~ 94.9596Qn1), 7 = 0.935 @) TEMP AA A, BL NCL) FL ns fy 8 BR BZA eA HE HH K 2 PRM RICE (No.l FE Nos} FFM HCHAR ES TRF OZ A Qring SHEN BLS, A 1) = -116.95144 — 370.89633Qring, 7 = 0.974 (2) TA) 2B fa Sj He oc BR Yap ZA AT AAI A HE een aR (2) EA Ye a EG AT He, HRT RIAL SH Hy 0.2% . 2.3%. -19% . 04%. 3.2 SUR a ete MNDO 5 2 i S4-2e OH, AE Bk HAT A 7 HE BI i HF AASB (HOMO) FUSE AR ZS FAI (LUMO) (HE BAR P, Wi. MHS ETL, RPP RR, 2- ROK ME, Aq FAA RR ME, 4 PRE 5 FROM FRE RA, RRA RRS AP, PA, RRA FAME Pp MAA RMA DA FO ARE FES 1 ae. DABS 1a) TL, ike 4 2 Ay HOMO 45 Fe ff) LUMO Xt aR ME MIIC RC, BaP SU. WATERS . ete ao mT ay A fe a Fe ARH d BLE Adhd) AE AM LUMO 45 Fe fy HOMO 3 HE BAN, ATLA EAD Fe Hf HAE LY dF BA te HG St F 1S Pb. A EA “ o PAGEL, HA Tie ae BF Oe RR Fig.1 The schematic of orbital symmetry ERLE, MRR AZ BL, PRR AO HE OY PT, BRANDT HEU KO BRIE AT Od TA ia AE EAP Bb Ag SA BS A 3.3 SLUR ae Deo aE Me EAE AO Ae 2 Aa, ERE cfm Sek Hy ATR Sh PA ER BR, be AMIR i MERA RIA, HAI, PIEZO TE eR SCPE HLF AA SR fh FAL 96 8 BA) Re FP A th PAL ME, SA ri BE Rh A UBB AR GAVE 1 HSE a I —3m PRRT: TIMEARAKLAWORT SOS RMA ORK 199 RRL, RR IKE, 4 ES BORK HRS ARAM RAR. C 5 Fe WAAR AANA REPL A MH BR, RARER. Ri, 3 09 22 OR EEK, 2- FRE, 4 BRR MME AB IE. BRT OB At OR a fay Nak — BE AE Shy BAM NTE SF CMRP LEAR BR, SMA, SOFIE IRAE Fe J TH Om AT FRKKELSWHEX, ASKHOFEMRAMBMM, HERKEN OMT RA 0.4615 1.6021 x10-9C fy Hah. EC AY BL a AH SR HE Sh YY, SATE HY the UE Fe ARF GAT, AB Fak A Sd EH aR By, ET a Eo TRH. 34 KPLSAELAHRMERSEHSRHLR KVESRELAAS TOP REAM, RE ON a £—‘% CHs ff) HR ~SO3Na WRAL. Hit HAT 1, 26752 Enomo HRA IN, ii ZLumo HR aH. FEW BS FeRAM A AK, wT RE A Ee — TA. Bb, APE RE, PTAA TS 2TN RF IH LM a = EA BA (2 4 -CHs, —* nie ne “CH: ~ CH.SO3Ne A, AF HT EE RE Fe Hm AT ABI OHA. MA CNDO/2 eit RH, KTVT PRT RT BZ AW 0.0621 x 1.6021 x10-19C, Tag BE Hh AK RH #4) 2 0.0830%1.6021 x10-'9C, fil 2 I TE He A He eat >, Pat a aE AS Pe we BR TT HA He Fa a BR. OYE RE RE te a ae age, ZTRKBRM 2, ROTRASRKAARAKEH, MK, HHH CoN R B.A eH mes TO EER SEM RAR. B MNDO HLH SE. HM $A -0.2618x1.6021 x10" 9C, ff O MAF HHH -0.9727x 1.6021x10- °C , OMFAARE RM, BS Ht A, Mie HE RR. ), ME OAS Fe FR HE AEB) 2 (ol A. AIR RIE es * x wt LMR, RIF. fh SOF HR, 1995, 15(3): 229 2 Pa. a, Wa, RAR, A. EHR, 1994, 52: 620 3 Pople J A, Beveridge DL. , Li. “SF MMEM ABI”, IER: HAMMEL. 1978. p.117 AHR BPR. ERS RTM”, A: BE HIAR AL, 1985. p.233.200 FS BH A 16% A STUDY ON CORRELATION BETWEEN ELECTRONIC STRUCTURE AND INHIBITION PROPERTIES OF FIVE-MEMBERED DINITROGEN HETEROCYCLIC COMPOUNDS LUO Mingdao YAO Luan WU Qingyn YAN Xiaoci YU Xiaodong ZOU Jingyun OUYANG Li (Dept. of Chemistry, Dept. of Environmental Science, Wuhan University) ABSTRACT ‘The inhibition efficiencies of imidazole and its derivatives, analgen, and amidopyrine for mild steel in hydrochloric acid were determined with weight loss method. ‘The geometries of imidazole and its derivatives were optimized, and the energies and coefficients of their molecular orbitals were calculated using semiempirical MNDO method. Approximate ground-state electronic properties of analgen and amidopyrine were obtained by means of MNDO and CNDO/2 methods. [t was found that the sum of net charges of five atoms in the ring for imidazole and its derivatives was well correlated with their inhibiting efficiencies. ‘The mechanism of inhibition process was discussed with quantum chemistry. KEY WORDS Imidazole and its derivatives, Inhibition, MNDO method RRR RRR RRR RRR RRR RRR RRR RRR ED

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