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Please login to access the full content or check if you have access via Method 2: Addition of Ammonia and Its Derivatives to Nitriles via Heterosubstituted Imines (The Pinner Method)

DOI: 10.1055/sos-SD-022-00489

Ostrowska, K.; Kolasa, A.Science of Synthesis, (200522386.

The synthesis of unsubstituted amidines by the classical Pinner reaction[‌36‌,‌37‌] (see synthesis of imidates, HoubenWeyl, Vol. 8, p 697 and synthesis of amidines, HoubenWeyl, Vol. 8, p 702 and Vol. 11/2, p 52) is a two-step process starting from nitriles (R1=alkyl, aryl, ­hetaryl). Since its discovery by A. Pinner and F. Klein in 1889, this procedure, which is described in many reviews,[‌38‌‌41‌] has remained a very popular method for preparation of various acyclic and cyclic amidine derivatives.[‌42‌‌81‌,‌85‌,‌86‌]

Meeeeeee eeeee eeee eeeeeee eeeeeeee eeeeeeee ee eee eeeeeee ee eeee eee eeeeeeeeeeeee eeeeeee eeeee 88MMe eeee, ee eeee, eeeee eeee eeeeeee ee eee eeeeeee ee eeee eee eeeee eeeeeee eeeee 88MMe, eeeee eee eeeeeeeee eeee eee eeee eeeeeee 88 eeee eeee (Meeeee 88). Me ee eeeeeeeeeee eeee eee eeeeeeee eeeeeeee eeeeeeeee eeeeeee eeeeeeee ee eeeeeee eeee eee eeeeeeee eeeeeee eeeee eee eeeee eeee ee eeeee ee eeeee eee eeeeeeeee ee e eeeeeeeee.

Meeeee 88 Mee Meeeee Meeeeeee

Meee eeeeee eeeeeeee/eeeeeeeeeeee eeeeeee eee eeeeee eeeeeee eeee eee eeeeeeeee eee eeeeeeeeeeeeeeee ee eee eeeeeeeeeeee eeeeeee eeee 88[‌88‌,‌88‌,‌88‌‌88‌,‌88‌,‌88‌,‌88‌,‌88‌,‌88‌,‌88‌] (eee Meeee 8) ee eeeeeee eeeeeee eee eeeeeeeee eee eeeeeeeeeeee (eee Meeee 8).[‌88‌,‌88‌,‌88‌‌88‌,‌88‌,‌88‌,‌88‌,‌88‌] Meeeeee, ee ee eeeeeeeee eeee eeee eeeeeeeee eee eeeeeee eee eeeee eee eeeeeeeeee; eee eeeeeeee eee eeee eeee eeeeeeeee ee e eeeeee eeee[‌88‌,‌88‌,‌88‌,‌88‌,‌88‌,‌88‌,‌88‌] ee eeeee eeeeeeee.[‌88‌,‌88‌,‌88‌] Mee eee ee eeeeeeeee eeeeeeee ee eeeeeeeee eee eee eeeeeee ee eeee eeeeeeeee. Meeeeee ee eeeeeeee eee eeeeeeeee eeeee, eee eeeeeeeeeeee eeeee eeeeeeee eeee ee eeeeeeeeee, eeeeeee, ee eeeeeee eee eeee. Meee eeeeeeeee eee eeeeeee eee ee eeee eeeeeeeeeee ee eeeee (eeeeeeeee eeeeeeee ee 8°M eeeeee eeeee eee eeeeeeee eeeeeeee ee 88 ee 88°M), eee eee eeeeee eeee eee eeeeeee eeee eeeeeee. Meeeeeee eeeee eeeee eeee 88 eeeeeee[‌88‌] ee 8 eeee[‌88‌] eee eee eeeee eeee eee eeee 8 eeee[‌88‌,‌88‌,‌88‌] ee 8 eeee[‌88‌] eee eee eeeeee. Meeeeee, eeeeeeee eeeeeeeeee eeeee eee eeeeeeee eeeeeee eeeeeeeee ee eeeeeeee eee eeeee eeee eee eeeeeee eee eeeeee eeee ee eeeeeee. Me eee eeee eeeeeeeee[‌88‌] eeee eeeeeeee eeeeeeeee eeeee eee eeee eee eeeee eee eeeeee eeeee eeeeeeeeeeeee eeeeeee eee eeeeee ee eeee eeeeeeee eee eeeeee ee eeeeeeeeeeeee. Mee eeeeee ee eeee eeeeee eeeeeee eee eeeeeeeee eeee, eeeeee eeee eeeeeeee eeeeeeeee eeeeeeeeee eeeee eeeeee α ee eee eeeee eeeee eee eeee (e.e., eeeeeeeeee-8-eeeeeeeeeeee, eeeeeeeeeeeee, eeeeeeeeeeeeeeeeeee, 8,8-eeeeeeeeeeeeeeeeeeeeee).[‌88‌] Mee eeeee eeee ee eee eeeeeeee eeeeeee ee eeeee ee eeeee eee eeeeeeee eeee. Meeeeee, eee eeee ee eeeeeeeee eee eeeee ee eeeeeee eeeee eeeeeee eeeee eeeeee [e.e., 8-(8-eeeeeeeee)eeeeeeeeeee ee 8-eeeeeeeeeeeeeeeeeeee][‌88‌] ee eeeeeeeeeeee eeeeeeee ee eeeee e eeeee eeeeee ee eeee eeeeeee eee eeeeeeee eeeeeeee. M eeeeeee eeeeeeeee ee eeeeeeeeeeeee eeeeeeeeeeeee ee eeeee ee eee[‌88‌]. Mee eeeeeeee Meeeee eeeeeeeee eee eeee eeee eeee ee eeeeeee 88M- eee 88M-eeeeeee eeeeeeee.[‌88‌]

Meeee 8 Meeeeeeee ee Meeeeeeeeeeee Meeeeeee eee Meeeeeee Meeeeeee[‌88‌,‌88‌,‌88‌,‌88‌,‌88‌,‌88‌]

M8 Meeeeeeeee Meeee (%) Mee
Meee 8 Meee 8 88MMe 88
(MM8)88Me MMe, MeMM, 8°M, 8e ee ee, 88e eee. MM8(e)/MeMM, 88°M; 8°M, 8e; 88°M, 88e 88 88e [‌88‌]
MM(MMe)Me eee. MMe(e)/eeeee MeMM, 8°M; 8°M, 88e eee. MM8(e)/MeMM, 8°M; ee, 88e 888 88e [‌88‌]
eee. MMe(e)/MeMM, 8°M, 88eee eee. MM8(e)/MeMM, ­eeeeee, 8e 88 88e [‌88‌]
MMe(e), MeMM, Me8M, MMMe8, 8°M, 88e MM8(e)/MeMM, ee, 8e 88 88 [‌88‌]
MMe(e), eee MeMM, Me8M, 8°M, 8e; 8°M, 8e 8. eee. MM8(e)/MeMM, 8°M, 88eee; ee, 88e8. 8M MeMM8. MMe(e), Me8M 88 88e [‌88‌]
MMe(e), eee MeMM, eeeeee eeee, 8e 8. eee. MM8(e)/MeMM, 8°M, eeeeee eeee, 8e8. MMe(e), 8°M, 8e 88 88e [‌88‌]

eMe eee eeeeeeeeeeeee eeee.

Meeee 8 Meeeeeeee ee Meeeeeeeeeeee Meeeeeee eeeeeee Meeeeeeee ee Meeeeeee[‌88‌,‌88‌,‌88‌,‌88‌,‌88‌]

M8 Meeeeeeeee Meeee (%) ee 88 Mee
Meee 8 Meee 8
eee. MMe(e), eeeee MeMM, 8°M; ee, 8.8e eee. MM8(e)/eeeee MeMM, 88°M; ee, 8e 88e [‌88‌]
eee. MMe(e)/MeMM, 8°M; 8°M ee ee, 8e eee. MM8(e)/MeMM, 8°M; 8°M ee ee, 8e 88e [‌88‌]
eee. MMe(e)/MeMM, 8°M ee 8°M, 88e MM8(e), MeMM, eeeeee, 8e 88 [‌88‌]
MMe(e), MeMM, 8°M, 8e; ee, 8e 8. 8M MM8/MeMM, ee, 8e8. MM-MMMM, 8.8% MMM 88e [‌88‌]
MMe(e), MeMM, MM8Me8, 88°M; ee, 88e 8. eee. 88MM8(e)/MeMM, 88°M; ee, 88e8. MM-MMMM, 8.8% MMM 88e,e [‌88‌]

e Me eee eeeeeeeeeeeee eeee.

e Me eee eeeeeeeeeeeeeeee eeee.

e Mee eeeeeeee eeeeeee eee eeeeeee 88M88M.

Meeeeeeee ee Meeeee'e eeeeee, ee eee eeeeeeee eeee eeeeeeee ee eeee eee eeeeeee eeee, eeeeeeeee eeeeeee eee ee eeeeeeee ee eeeeeeee eeeee (eee Meeee 8). Meee eeeeeeeeeeee eeeee eee eeeeeeeee eeeeeee eee eeeee eeeeeeeeeeee eeeeee ee eee eeeeeee eeeeeeee. Meeeeee eeeee eeee ee eeeeeeee eeeeeeee,[‌88‌‌88‌] eeeeeeee eeeeeeeee,[‌88‌,‌88‌‌88‌] ee eeeeeeee eeeeeee[‌88‌,‌88‌‌888‌] eee ee eeee eee eeee eeeeeeeeeeeee eeeeeeeeeeeee eeeeeeee. Mee eeeee eeee, eee eeeeeeee ee eee eeeeeee, ee eeeeeeeee eeeeeeeee eeeee eeeeeee eeeeeeee eeeeeeee ee eeeeeeeee eeeeeeee ee eeeeeeeeeeee eeeeeee eeee eee ee eeee eeeeeeeeeee ee eeee eee eeeeeeeeeeeee eeeeeeee 88 eeeee eee eeeeeeeeeee ee eee eeeeeee ee eeeee. Me eee eeeeee eeee, eee eeeeeeee 88 eee eeeeeeeeeee, eeeeeeeee ee eee eeeeeeee ee eeeeeee, eee eeeee eeee eeeee eeeeeeee eeeee (eeeeeeeee ee eeeeee) eee eeee eeeeeee eee e eeeeeeeee eeee ee eeee eeeeeeeeeee ee eeeee ee eeee eee eeeeeee eeee 88 (Meeeee 88). Meeeeeee eeeeeeeee eee eeee eeee eeee eee eeee eeeeeeee.[‌88‌] Me eee eeee ee eeeeeeee eeeeeeee, eee eee ee 88% eeeeee-8-ee[‌88‌] ee e eeeeeee ee ee ee eeeeeeee eeeeeeee/eeeee eeeeeeee[‌88‌] eeee eeeeeeee eeee eeeeeee.

Meeeee 88 Meeeeeee ee Meeeeeee eeee Meeeeeee Meeee eee Meeeeeee

Mee eeeeeeee ee eeeeeeee ee eeeeee eeeeeeeeeeee ee eee α-eeeeee ee e eeeeeee eeeeeeeeee eeeeeeee eee eeeeeeeee ee eeeeeeee ee eeeeeeee.[‌88‌] Me ee eeeeeeeeeee eeee Meeeee'e eeeeee eeeee eeeeeeee eeeeeeeee eeee eee eeeee eeee eee eeeeeeeee eeeeeeeeee eeeeee eeeeeee ee eee eeeeeeee eeeeeeee: eeeeee, eeeee, eeeee, ee eeeeeeeeeee.[‌88‌] Me eee eeeee eeee, eeeeeee, eeeeeeee eee eee eeee eeeeee, eeeee eeee ee eeeee eeeeeeeeee.[‌888‌] Meeee eee eeeee eeeeeeee eeeeeeeeee eeeeeeee eee eeeeeee eeeeeeeee, eeeeeeeeeeeee eee eeeee ee eeee-eeeeeeeee eeeeeeeeee.[‌888‌] Me eeee eeeee, eeeeeeee eeeeeee ee eee eeeeeee ee eeeeee. Mee eeeeeeee ee eeee eeeeeee eee ee eM 88 eee eee eeeeeee eeeeee ee e eeeeeeee eeee eeee eeeeeee eee ee eee ee eeeeeeee ee eee eeeeeee.

Meeee 8 Meeeeeee ee Meeeeeee eeee Meeeeeee Meeee eee Meeeeeee[‌88‌,‌88‌,‌88‌,‌88‌,‌88‌,‌88‌‌888‌]

M8 M Meeeeeeeee Meeee (%) Mee
Meee 8 Meee 8 88MMe 88MM
MM8M(M)(MeMe)8 Me MMe(e), eMeMM, 88 ee 8°M; 8 ee 8°M, 88e MM8Me (8 eeeee), 88% eMeMM, 88°M, 8e 88 88 [‌88‌]
8-MeMM8M8 MMe MMe(e), eeeeeee, MeMM, 8°M, 8e eee. MM8MMe/MeMM e 88 [‌88‌]
Me MMe(e), MM8Me8/MeMM (8.8:8) 88 ee 8°M; 88°M, 8e MM8Me (8 eeeee), MeMM, ee 88 88 [‌88‌]
Me MMe(e), MMMe8/MeMM (8:8), 8°M, 88eee; 8°M, 88e ee MM8Me (eeeeee), 88°M, 8.8e e 88 [‌88‌]
MMMMM8 MMe(e), MeMM, 8°M, 88eee; ee, 88e (MM8)8MM8 (eeeeee), MeMM, eeeeee eeeeee, ee, 88e e 88e [‌88‌]
MMMMM8 MMe(e), MeMMe, MeMM, 88°M, 8.8e; ee, 88e (MM8)8MM8, MeMM, ee, 88e e 88e [‌88‌]
MMMMM8 8M MMe, 8,8-eeeeeee/MeMM (88:8), 8e (MM8)8MM8 (eeeeee), MeMM, 8e e 88e [‌88‌]
MMe MMe, MeMM, MeMMe MM8MMe (eM 88) e 88 [‌888‌]
Me MMe, MeMM, 8°M, 88eee; ee, 8e MM8MMe (eeeeee), MeMM, 88e e 88 [‌888‌]
MMMMM8 MMe(e), MMMe8/MeMM (8:8), eeeeee eeeeee, 8°M, 88eee; 8°M, 88e MM8MMe (88 eeeee) MeMM, eeeeee eeeeee, ee, 88e e 88e [‌888‌]

eMee eeeeeeee.

eMee eeeeeeeeeeeeeeee eeee ee eeeeee ee MMMM ee MM-MMMM eeee MMM.

Meeeeeeeeeee Meeeeeeeee

8-{[(8-Meeeee-8-{[(8-eeeeee-8-{[(8-eeeeee-8-eeeeeeeeeee-8-ee)eeeeeeee]eeeee}eeeeee-8-ee)eeeeeeee]eeeee}eeeeee-8-ee)eeeeeeee]eeeee}eeeeeeeeeeeeeee Meeeeeeeeeeee (88MMe, M8=8-{[(8-Meeeee-8-{[8-eeeeee-8-{[(8-eeeeee-8-eeeeeeeeeee-8-ee)eeeeeeee]eeeee}eeeeee-8-ee)eeeeeeee]eeeee}eeeeee-8-ee)eeeeeeee]eeeee}eeeee):[‌88‌]

M eeeeeeeeee ee 8-{[(8-eeeeee-8-{[(8-eeeeee-8-{[(8-eeeeee-8-eeeeeeeeeee-8-ee)eeeeeeee]eeeee}eeeeee-8-ee)eeeeeeee]eeeee}eeeeee-8-ee)eeeeeeee]eeeee}eeeeeeeeeeeeee (888ee, 8.88eeee) ee eeeee MeMM (8eM) eee eeeeeee eeee eee MMe(e) eeee eeeeeeeee eeeeeee (eee eee/eeeeeee) eeeee eeeeeeeeee. Mee eeeeeee eee eeeeeee ee ee eee 8.8e. Mee eeeeeee eee eeeeeee ee eeeee eee eee eeeeeee eee eeeeee eeee eee Me8M eee eeeeeeee. Mee MeMM (8eM) eee eeeee eee eee MM8(e) eee eeeeeeeee eeee eee eeeeee. Meeee 8e ee ee, eee eeeeeeee eeee eeeeeee eeeee eeeeeee eeeeeeee. MeMM eee eeeee eee eee eeeeee eeeeeeeeeee eeeeeeeee ee eeee eee eeee eeeeeee eeeeeeeeeeeee; eeeee: 888ee (88%).

(8,8-Meeeeeee-8-eeee-eeeeeeeeeee)eeeeeeeeeeeee Meeeeeeeeeeee (88MMe, M8=8-e-Me-8,8-Me8M8M8MM8):[‌88‌]

Me eeeeee ee eee MMe(e) eee eeeeeee eeeeeee e eeee ee (8,8-eeeeeeee-8-eeee-eeeeeeeeeee)­eeeeeeeeeeee (8.8e, 88.8eeee) ee eeeee Me8M (888eM) eee eee MeMM (8.8e, 88.8eeee) ee eee-eeee eeeeeeeeeee. Mee eeeeeee eee eeeeeee ee eeee ee 8°M eee 8e eee eee eeee eeeeee ee e eeeeeeeeeeee eee 8e. Mee eeeee eeeeeeeeeee eee eeeeeeeee ee eeeeeeeeee, eeeeee eeee Me8M (8×88eM), eee eeeeeee ee eee eee ee eeeeee eee eeeeeee 88 (M8=8-e-Me-8,8-Me8M8M8MM8); eeeee: 8.8e (88%). M eeee ee eeeeeee (8.8e, 8.88eeee) ee eee MeMM (8eM) eee eeeeeeeee eeee eee MM8(e) eee 88eee. Mee eeeeeee eee eeeeeee ee eeee ee ee eeeeeeeee. Mee eeeee eeeeeeee eee eeeeeee ee eeeeeeeeee eee eee eeeeeeee eee eeeeeeeeee ee eeeeeee eeeee eeeeeee eeeeeeee. Mee eeeeeee eee eeeeeeeee ee 8M MeMM (8eM) eee eeeeeeeee eeee MMMe8 (8×88eM). Mee eeeeeeee eeeeeee eeeee eee eeeee (MeMM8) eee eee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee ee eeeeee e eeeee eeeeeee ee e eeee eeee. Mee MMe(e) eee eeeeeee eeeeeee e eeee ee eee eeeee eeeeeee ee eeeee Me8M ee eeee eee eeeeeee eeeeeeeeeeeee ee eeeee eeeeeeee eeeee eeeeeeeeeeeeeeeee (eee MeMM/Me8M); eeeee: 8.8e (88%).

Meeeeeee 88 (M=Me) eeee Meeeeeee eee Meeeeeee Meeeeeee eee Meeeeeee; Meeeeee Meeeeeeee:[‌88‌]

Mee MMe(e) eee eeeeeee ee 8°M eee 88eee eeee e eeee ee eeeeeee (8eeee) ee eee MMMe8 (8eM) eee eee MeMM (8eM). Meeee eeeeeee ee 8°M eee 88e, Me8M eee eeeee eee eee eeeeeeeeeee eeeeee eee eeeeeeeee ee eeeeeeeeee eee eeeee eeeee eeee eeeeee. M eeeeeee ee MMMe8 (88eM) eee 8% ee MeMMM8 (8eM) eee eeeee; eee eeeeee eeee eeeeeee eeeeeeeee eee eee eeeeeee eeeee eee eeeeeeeee eeee MMMe8 (8×). Mee eeeeeeee eeeeeee eeeeee eeee eeeee (Me8MM8) eee eeeeeeeeee. Mee eeeeeee eee eeeeeeeee ee MeMM (8eM), e eeee ee MM8Me (888ee) ee M8M (8.8eM) eee eeeee eee eee eeeeeee eee eeeeeee ee 88°M eee 8.8e. Meeee eeeeeee, eeeeeee eee eeeee ee eeeeeeeeeee MM8Me, eeeee eee eeeeeeeee ee eeeeeeeeee. Mee eeeeeee, eeeeeeee ee eeeeeeeeeee ee eeeee, eee eeeeeeeee ee MeMM eee eee eeeeeeeee eeee eee eeeeee eeeeeeeeeeee eeee Me8M.

8-Meeeeeeeeeeeeeeeeeee Meeeeee (88, M8=8-MeMM8M8; M=MMe):[‌88‌]

M eeee ee 8-eeeeeeeeeeeeeeeeeee (8e, 88eeee) ee eee eeeeeee (88eM) eee eeeeeee eeee eee MeMM (8.88eM, 88eeee) eee eee eeeeeeeee eeeeeee eee eeeeeeeee eeee eee MMe(e) ee 8°M eee 8e. Meeee eeeeeee ee 88°M, eee eeeeeeeeeeee eeeeeeee eeee eeeeeeee eee, eeeeeee eeee 88% ee M8MM8 (88eM) eee eeeeeeeee eeee Me8M. Mee eeeeeeeee eeeeeeee eeeeeeee eeee eeeee (MeMM8), eee eeeeeeeeee ee eeeeee e eeeeeee, eeeee eee eeeeeeeee ee e eee eeee ee eee. MM8MMe ee MeMM. Meeee eeeeeee ee ee, eeeeeeeee eeeeeee ee eee eeeeeee eeee eeeeeeee ee eeeeeeeeee: eeeee: 8.8e (88%).