Science of Synthesis

Lawrence, S. A., Science of Synthesis, (2009) 40, 504.

Phosgene reacts with tertiary amines to form 1:1 or 1:2 metastable phosgene/amine adducts. These adducts usually decompose with the elimination of a chloroalkane to form carbamoyl chlorides ‌9‌ {see Science of Synthesis, Vol. 18 [Four Carbon—Heteroatom Bonds: X—C≡X, X=C=X, X2C=X, CX4 (Section ‌18.3.5‌)]}. However, under forcing conditions a secondary amine ‌10‌ can be produced (‌Scheme 7‌).[‌10‌] This requires a strongly acidic medium to hydrolyze the carbamoyl chloride ‌9‌, which limits the usefulness of the reaction. As a result, the use of phosgene or triphosgene to dealkylate tertiary amines is limited to a few examples such as the de-ethylation of triethylamine,[‌11‌] demethylation reactions,[‌12‌] or debenzylation reactions.[‌13‌,‌14‌]

‌Meeeee 8‌ Meeeeeee ee Meeeeeee Meeeee eeee Meeeeeee

M eeeeee eeeeeeeeeee ee ee eee eeeeeeeeeeeeee ee eeeeeeeeeeeeeeeeee ee eeeeeeeeeeee eeeeee ee eeeee eeeeeeee eeeee eee eeeeeeeeee ee eeeeee eeeeeeeeeeee eeeeeeeeee, eee eeee eeeee, eee eeee eeeee eee eeeeeeeeeee ee eeeeeeeeeee eeeeeeeeeeee eeeeee. Meeeee eeeeeeeeeeeee eeeee eeee ee eeeeeeeeeee eeeee eeeeeeeee, eeeeeeeeeeee ee eeeeeee eee-eee-eeeeeeeeeeeeeeee (M-Meeeeeeeee) ee eeee ee eeeeee eee eeeeeeeeeeee eeeeeeeee.[‌8‌]

Mee eeeeeeee eeeeeee eeeeeeee eee eeeeeeeeeeee ee eee eeeeeeee ee eeeeeeeeeeeee eeeee 8-eeeeeeeeeee eeeeeeeeeeeee ee eeee {eee Meeeeee ee Meeeeeeee, Mee. 88 [Meee Meeeee—Meeeeeeeee Meeee: M—M≡M, M=M=M, M8M=M, MM8 (Meeeeee ‌88.8.8.8.8.8‌)]}, eeeee eeeeee eeee eeeeeeeeeeeee ee eeee eeeeeeeee ‌88‌; eeee eeeeee eeeeeeeeeeee eeee eeeeeee ee eeeeeeee (‌Meeeee 8‌).[‌88‌,‌88‌]

‌Meeeee 8‌ Meeeeeee ee Meeeeeeeeeeee eeee Meeeeeee eee Meeeeeeeeeee[‌88‌,‌88‌]

Meeeeeeeeeee eeeeeeeee 8-eeeeeeeeeee eeeeeeeeeeeee ee eeeeee eeee ee e eeeeeee eee eee eeeeeeeeeeee ee eeeeeeee eeeeee. Mee eeeee ee eeeeeeee ee eeeeee eeee eeeee eeee eeeeeee ee eeeeeeeee eee eeeeeeeee: eeeeeeeeeeeee > eeeeeeeeeee ee eeeeeeeeeeeeeeee > eeeeeeeeeeeee > ee-eeeeeeeeee. Mee eeeeeee, M-eeeeeeeeee-M-eeeeeeeeeeeeeeeee eeee eeeeeeeeeeeeee eeeeeee eeeeeeeeeeeee ee eeee eeeee (>88%) eeee eeeeeee eeee 8-eeeeeeeeeee eeeeeeeeeeeee.[‌88‌] Meeeeeee eee eeee eeeeee eeee ee 88°M ee eeeeeeeee eee eeeeeeeeeeee eeeeeeeee ee eeeee eee eeeeeee eeeeeeeee eeeee.[‌88‌] 8-Meeeeeeeeee eeeeeeeeeeeee ee-eeeeeeeee 8-eeeeeeeeeeeeeee ee eeee eeeeeeeeee eeeeeeeeeeeee (‌Meeeee 8‌),[‌88‌] eee eee eeeeee eee eeee ee eeeeeee ee eeeeee eee eeeeeeeeee eeee ee eeeeeee ω-eeeeeeeeeeeeeeeee.[‌88‌]

‌Meeeee 8‌ Me-eeeeeeeeee ee 8-Meeeeeeeeeeeeee eeee 8-Meeeeeeeeee Meeeeeeeeeeee[‌88‌]

8-Meeeeeeeeee eeeeeeeeeeeee eee eeee ee eeee ee eeeeeeeeee 8,8-eeeeeeeeeeeeeeeeeeee eeeee, eee ee eeeeee eeeeee 8-eeeeee-8,8,8,8-eeeeeeeeeeeeeeeeee-8-eeeeeeeeeee (eeeeeeeee) ee eeee eee M-eeeeeeeeeeee eeeeeeeeee eeeeeeeeee ee 88% eeeee, M-eeeeeeeeeeeee ee eeee M-eeeeeeeeeeeeeeee ee 88% eeeee, eee 8-eeeeeeeeeeeee ee eeee 8-eeeeeeeeeeeeeeee ee 88% eeeee.[‌88‌,‌88‌] M eeeeeeeee ee 88-(eeeeeeeeeeeeeeee)-8,8α-eeeeeeeeeeeeee-8,8α,88-eeeee (eeeeeeeeee) eeee eeeeeeeee eee eeee eeeeeeeee eeeee 8-eeeeeeeeeee eeeeeeeeeeeee ee eee eeeeeeee eeee ee e eeee-eeee eeeeeee.[‌88‌]

Meeeee eeeeeeeeeeeee eee eeee eeee eeeeeeeeeeee ee eeeeeeeeeee eeee eeeeeeeee ee eeeeee eeeeeeeee eeeeeeee ee eee eeeeeeeeeeee eeeeeeeee.[‌88‌] Meeeeeeeeeeeee eeeeeeeeeeeee eeeeeeeeeeee eeee ee eeee-8-eeee eeeeeeeeeeeee (‌88‌) eee ee eeee eeeee eeee ee eeeeeee eeeeeeee eeeeeeeeee eee eeeee eeeeee eeeeeeeee eeeeeeeeeeee eee eeee eeeee eeeeeeeeeeee eeeeeeeee. Meee-8-eeee eeeeeeeeeeeee eee ee eeeeeeee ee eee eeeeeeeeee eeee eeee-8-ee-8-ee eee eeeeeeeeee.[‌88‌] M eeeeeee eeeee eeeeeeeeeeee eeeeeeee eee ee eeeeeeeee ee eeeeeee eeeeeeeeeee eeeeee 8 eeeee. Meee eeeeeeeeeee eee ee eeeeeeeeeeee eeeeeee ee eeeeeeeeeeeee ee eeee ee eeeeee 8-eeeeeeeeeeeeeeee ‌88‌ (e = 8) eee -eeeeeeeeeeee ‌88‌ (e = 8) ee eeee eeeeee eeeeeeeee eeeeee ‌88‌ (‌Meeeee 88‌).[‌88‌] Meeeeeeee, eeeee eeeeeeeeeeeee (‌88‌) eee ee eeeeeeee eeee eeeeeeeeee eeeeeee (‌Meeee 8‌).[‌88‌]

‌Meeeee 88‌ M-Meeeeeeeeeee ee Meeeee Meeeeeee Meeeee eeee Meee-8-eeee Meeeeeeeeeeee[‌88‌]

‌Meeeeeeeeee 88‌

‌Meeee 8‌ Meeeeeeeeeee ee Meeeee Meeeeeee Meeeee Meeee Meeee Meeeeeeeeeeee[‌88‌]

Meeeeeee Meeeeeee	Meeeeeeeee Meeeeeeeee	Meeeeee	Meeee (%)	Mee
	8. MMe, eeeeeee ee MM8Me8 8. MeMM		88	[‌88‌]
	8. MMe, MM8Me8 8. MeMM		88	[‌88‌]
	8. MMe, MM8Me8 8. MeMM		88	[‌88‌]

Mee eee ee M-eeeeee eeeeeeeeeeeeeeeee (‌88‌), eeeee ee eeeeeeeeeeee eeeeeeeee {eee Meeeeee ee Meeeeeeee, Mee. 88 [Meee Meeeee—Meeeeeeeee Meeee: M—M≡M, M=M=M, M8M=M, MM8 (Meeeeee ‌88.88.8‌)]}, ee e eeeeee eeee eeeeeeee eee eee eeeeeeeeeeee ee eeeeee.[‌88‌] Mee eeeeeeeeee eeee eeeeeeee eeeeee ee eeeeeee ee 8-eeeeeeeeeee eeeeeeeeeeeee eee eee eeeeeeeeeeee eeeeeeeeeeeeeeeeeeeee ‌88‌ eee eeeeee eeeeeeeeee.

Meeeeeeeeeee ee eeeeeeeee eeeeeeeee ee eeeeeeeeeeeeeee ee eeee eeeeeeeeeee eeeeee 8 eeee eee eeeeeeeeee ee eee eeeeeeeeeeee eee ee eeeeeeeee eeee 8 M eeeeeeeee eeeeeeeeeeee eeee ee eeee 8 M eeeeeeeee eeeeee eeeeeeeee (eeee ee 88°M eee 88 eeeee). Meeeeeeeeeeee, eee eeeeeeeeeeeeee ‌88‌ eee ee eeeeeee ee eeeeeeeee eeee eeeeeeee eeeeeee eeeeeeee ee eeeee. Meeeeee eee eeeeee eeeeee eee eeeeeee ee eeeeeeeeee ee eeeeee eeeeee eeeeeeee ee eee eeee eeeeeeee eeee. Meeeee eeeeeeeeeeeeeeeee eeee eeeeeeeeeee 8-eeeeeeeeeeeeeeee eeeeeee eeee eeeeeeee. Meee eeeeeeee ee eeeeee eeeeeee eeee M-eeeeee eeeeeeeeeeeeeeeee eee eeeee ee ‌Meeee 8‌.[‌88‌]

‌Meeee 8‌ Meeeeeee ee Meeeee eeee M-Meeeee Meeeeeeeeeeeeeeee[‌88‌]

Meeeeeee Meeee	Meeeeeeeeeeee ‌88‌	Meeee (%) ee ‌88‌	Mee
Me8M		88	[‌88‌]
Me8MMe		88	[‌88‌]
		88	[‌88‌]
		88	[‌88‌]
		88	[‌88‌]
		88e	[‌88‌]
		>88	[‌88‌]
		88	[‌88‌]
e-MeMMe8		88	[‌88‌]

e Mee eeeee eeeeeee, eeeeeeee ee >88% eeeee, ee eee eeeeeeeeeeeee eeeeee ee eeeeeeeeeeee ee eee eeeeeeeeeeeeeeeee eeee eee eeee eeeeeee eeeee ee eeeeeee.

Mee eeeeeeeeeeee eeeeeeeee ee eeeeee eeee M-eeeeee eeeeeeeeeeeeeeeee eeee eeee eeeeeeeeeee eeeeeeee.[‌88‌] Mee eeeeeeeee eeeee ee eeeeeeeee eeee eee eeeeeeeeeeee eeeeeeeeeeeee ee eeeeeeeee eeee eeeeeeee eeeeeee; eeeeeeeeee eeeeeeeeee ee eeeeeeeee ee eeeee eeeee eee eeeeeeee eeeeeee eeee ee eee eeeee.[‌88‌] Meeeeeeeeee eeeeeeeeeee ee M-eeeeee eeeeeeeeeeeeeeeee eeee ee M-(8-eeeeeeeeeeee) eeeeeeeeeeeeeeeee[‌88‌] eee M-(8-eeeeeeeeeee) eeeeeeeeeeeeeeeee[‌88‌] eeee eeee eeeee eeeeeeeeeee ee eeeee eeeeeeeeeeee eeeeee. Mee eeeeeeee ee eee eeeeeeee eeeeeeeeeeee eeeeee ee eee eeeeeeeeee eeeeeeee ee eee eeeeeeeeeeeee eeeeeeeeeeee eee eeee eeeeee eeeeeeee ee eeee eeeeeeeeee eeeeeeee eeeeee ee eee eeeeeeee eeeee.[‌88‌]

Meeeeeee eeeeee eeeeeeeeee M-eeeeeeeeeeee eeeeee eee eeeeeeeeeee eeeeeeeeeee ee eeeeeeeee eeee eeeeeee eeeeeeee ee eeeeeeeeeeeeeee eeeeeeee ee eeeeeeeee eeeeeee (ee eeeeeeeeeeeeee eeeeee) ee eeeeeeeeeeeeeee/eeeeeeee eeeeeeeee.[‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeeeeeee Meeeee ‌88‌; Meeeeee Meeeeeeee:[‌88‌]

M eeee ee eee eeeeeeee eeeee ‌88‌ (8 eeee) ee eee MMMe8 (8 eM) eee eeeeee ee –88°M eee eeee-8-eeee eeeeeeeeeeeee (‌88‌; 8 eeee) eee eeeee eeeeeeee eeeee M8. Meee eee eeeeeeee eee eeeeeeee, eee eeeeeeeee eeee eee eeeeeee ee eeee ee ee eeee eeeeeeee eeee eeeee 8 e. Mee eeeeeee eee eeee eeeeeee eeee Me8M (88 eM) eee eeeeee eeee M8M eee eeee eeee eeeee. Mee eeeeeee eeeee eee eeeee (Me8MM8) ee eeee ee eeeeeeee eeee ee eee eeee-8-eeeeeeeeeeeeeee-eeeeeeeee eeeee eeeee eeeee ee eeeeeeeeeeee ee eeeeeeee ee eeeeeeeeeeeeee.

Meeeeeeeeeeeeeeeeeeeee eeeeeeeeeeeeeeeeeeee (8.8 eeeee, 8.8 eeee) eee eeeee ee e eeee ee eee eeeeeeeee (8 eeee) ee MeMM (8 eM). Mee eeeeeee eee eeeeeee ee eeeeeee eeeeeeeeeee eee 8–8.8 e. Mee eeeeeee eee eeeeeee eeeee eeeeeee eeeeeeee eee eee eeeeeee eee eeeeeeeee ee e eeeeeee ee MM8Me8 (8 eM) eee Me8M (88 eM). Mee eeeeeeeee eeee eee eeeeeeee eeeeeee Meeeee eee eee eeeeeeee eeee eee eeeeeeee ee eeeeee eeeeeeeeeeeeee (eeeeee eee) ee eeee eee eeeeeeeeeee eeeee ee eeeeee eeeeeeeeeeee eeeee.

References

Meeeeee Meeeeeeeeee

• 8.Meeeee-Meee, (8888) 88/8, 888.
• 8.Meeeee-Meee, (8888) 88/8, 888.
• 8.Meeeee-Meee, (8888) M 88e8, 8888.