Table 3.4 § values for the protons of CH;, Ch and CH groups attached to groups X, where R = alkyl and Ar = ary x CH3X R'CH)X R’R'CHX —R 09 13 LS ch, -cr” 13 a35 b3.0 \ N. 17 19 2.6 ==, ete. 18 (ie, end-of-chain) =, etc. 2.0 2.2 23 in-chain) — 20 — = 2.0 2.2 — COOR, —COOAr 2.0 21 2.2 —CN 2.0 25 27 —CONH;, —CONHR, —CONR; 2.0 2.0 21 —COOH 21 23 2.6 —COR 21 24 25 —COAr 25 2.8 1924 24 25 21 25 2.9 =e 22 3.1 42 —CHO 22 22 24 —Ph. Ar 23 26 29 —NHAr 25 3A —Br 26 33 44 —NHCOR, —NRCOR 29 3.3 3.5 —cl 3.0 34 4.0 —OR 3.3 33 3.8 + —NRy 3.3 34 35 —OH 34 3.6 38 —OCOR 3.6 4.1 5.0 —OAr 37 3.9 40 —OCOAr 30 42 St —NO, 4.3 44 16 F 43 _ Table 3.5 Influence of functional group X on the chemical shift position (6) of CHa. CH: and CH protons B to X. For B-shifis. add the following 10 the 8 values given in table 3.4 x CH, C~X CX CHC Xx —C=C OL 0.1 0.1 COOH. —COOR 02 02 02 —CN 0S 0.4 0.4 0.25 0.2 0.2 0.3 0.2 0.2 0.45 0.3 0.2 OL o Or 1.0 05 04 0.35 03 0.3 0.8 0.6 0.25 on on on 0.6 0.4 0 -OH, —OR 0.3 0.2 02 -—OCOR, —OCOAr O48 03 03 —OPh 04 0.35 03 —F 0.2 O48 ol —NO; 0.6 08 08Table 3.6 values for the protons of CH, (and CH) groups hes wre thar one f a1 substituent (modified Shoolery rules) Note xt for HC. ACH, = 12+ Ta ~‘, xt x an Less accurate for HC but we BCH = 15 + Ea x? x a a -= 075° —Ph 13 -= 0.9 —Br 1.9 —COOH, —COOR 0.7 a 20 12 —OR, —OH 17 10 —OCcOR 27 10 OPh 23 La Table 3.7 & values for H attached to unsaturated and aromatic groups 18 Ha Hx 24" —< Hy = Oco— 20 u 3.2" o 38 46 H 60 He OR a, 4.5-5.0 =< 6.57.5 R Me 6.2 1 ° (continued) * Alkyne proton signals removed on deuteriation, and valucs increased by a trace of pyridine33 5.0 33 6.2 68 7.0 1 (see table 3.9) y7a On ¥ 185 Or thiophene (cis or trans) H 4 \ NC Zs 7 RC. s 78 78 8.0 9.6 99Table 3.8 8 values for the protons of OH, NH and SH groups* ROH 0.54.5 higher for enols (11.0-16.0) lines often broadened ArOH 45 raised by hydrogen bonding to ~ 9.0 chelated OH, ~ 11.0 RCQOH 10.0-13.0 RNH,, RNHR’ 5.0-8.0 lines usually broadened ArNH,, ArNHR’ 3.5-6.0 occasionally raised; lines usually broadened RCONH,,RCONHR’ —5.0-8.5._lines frequently very broad, and even unobservable RCONHCOR™ 90-120 lines broadened RSH 1.0-2.0 ArSH 30-40 =NOH 10.0-12.0 often broadened *See notes on page 171. 1n of benzene protons (8 7.27) Substituent ortho = meta para —R 01S =01 -01 — +02 +02 +02 COOH, —COOR 408 4015 +02 -CN +03 +03 +03 —CONH, +05 +02 © +02 —CcOoR +06 +03 +03 —SR +01 -O1 02 —NH,, —NHR -08 -01S 04 —NICH,)2 =05 =02 =05 = +03 =02 01 —CHO +07 402 +04 —Br 0 0 o —NHCOR +04 -02 -03 —cl 0 0 0 —NH,* +04 402 © 402 or =02 -02 -02 OH =04 04 -04 —OCOR 402 -O1 02 —NO; +10 +03 +04 —SO,H,—SO,Cl,—SO,NH,.ctc. +04 +01 +0.1Table 3.8 8 values for the protons of OH, NH and SH groups* ROH 0.545 higher for enols (11.0-16.0) lines often broadened ArOH 45 raised by hydrogen bonding to = 9.0 chelated OH, = 11.0 RCOOH 10.0-13.0 RNH,, RNHR’ $0-80 lines usually broadened ‘ArNH,, AtNHR* 35-60 occasionally raised; lines usually broadened RCONH,,RCONHR’ = $.0-8.5_lines frequently very broad, and even unobservable RCONHCOR’ 90-120 lines broadened RSH 10-20 ArSH 30-4. =NOH 100-120 often broadened “See notes on page 171. Table 3.9 Shifts in the position of benzene protons (8 7.27) caused by substituents Substituent ortho = meta = para —CH;, —R —01S -01 0-01 -= +02 402 402 =COOH, —COOR +08 +015 402 -CN 4030 403 403 —CONH, +05 402 402 —COR +06 +03 403 —SR +01 -01 -02 —NH,;, NHR -08 =015 -04 N(CH); 05-02-05 -l +030 -02 0-01 —CHO +07 402 +04 —Br 0 0 0 —NHCOR 404-02 -03 —Cl o 0 0 —NH,* +04 +02 +02 OR -02 -02 —OH -04 04 —OCOR +02 -01 —NO; +10 +03 —SO,H, -S$0,C1, -SO,NH, et, +04 +0.)Table 3.10 Proton-proton spin-spin coupling constants Function Jade m, ws em) 10-18. depending on the electronegatvities oN ‘ofthe attached groups (commonly around: Hy TO ineydlohexanes, ets) depends om dihedral angle: see ection 3.9.2 Tor eyclohexanes, ete 11-19 (commonly around 14-16) I CO, (cis trans) 7 0-2 (for aromatic systems, 0-1) s 4 \=cH,—cH,=C" 13 N ortho, 7-10 meta, 2-3 ue {m on He a2 He Woon, { ‘he Se Soe 0.2 He 4, 1 Hz