Weygand/Hilgetag Preparative Organic Chemistry

9 58 Formation of new carbon-carbon bonds

JV-Semiacetals of formaldehyde, HOCH 2 NR 2 ,

718

and their esters

719

have

also been recommended for aminoalkylations; their use has given good results

even when side reactions otherwise occur, e.g., with naphthols.

Bohme and his co-workers^720 showed that reaction of #-halo alkylamines

(R = alkyl below) with compounds containing reactive methylene groups

amounts to aminoalkylation and affords Mannich bases that can be obtained

only with difficulty or not at all by other methods:

RR'N=CH 2 C1- + CH 2 XY > NRR'CH 2 CHXY + HC1

Such is the case also for JV-(halomethyl) carboxamides (R = H or alkyl,

R' = acyl)

721
and N-(halomethyl) diacylamides (R and R' = acyl), which
are specific for amidomethylation of /?-diketones, a reaction that cannot be
effected otherwise); for a review of these reactions see Gross and Hoft^679 ).

Amino- and amido-methylation of aromatic carbocyclic and heterocyclic

compounds by <%-halo amines and amides have also been reported.

707

*

722

'

723

Tscherniac-Einhorn condensation of reactive aromatic compounds with

(hydroxymethyl)-acyl- or -diacyl-amines also constitutes an amidoalkylation

and has been reviewed:

320

'

1060

'

724

ArH + C 6 H 5 CONHCH 2 OH > ArCH 2 NHCOC 6 H 5

Formaldehyde plus a nitrile may replace the (hydroxymethyl) amides; the
resulting reaction:

ArH + CH 2 O + RCN > ArCH 2 NHCOR

provides 7V-acylbenzylamines in one step directly from the aromatic com-

pound.^725

For alkylation by Mannich bases see page 970.

6. Sulfomethylation

Suter, Bair, and Bordwell

726

have described a reaction in which a hydrogen

atom is replaced by a sulfomethyl group. From 2-naphthol, formaldehyde, and

sodium sulfite they obtained sodium (2-hydroxy-l-naphthyl)methyl sulfate in

95% yield:

CH 2 SO 3 Na

CH 2 O + Na 2 SO 3 —>

(^718) H. Bohme, A. Dick, and G. Driesen, Chem. Ber., 94, 1879 (1961).
719
720 S. D. Ross, M. Finkelstein, and R. C. Petersen, /. Org. Chem., 31, 133 (1966).
H. Bohme, E. Mundlos, and G. Keitzer, Chem. Ber., 91, 656 (1958).
(^721) H. Bohme, R. Broese, A. Dick, F. Eiden, and D. Schunemann, Chem. Ber., 92, 1599
(1959); H. Bohme, A. Dick, and G. Driesen, Arch. Pharm., 294, 312 (1961).
(^722) H. Bohme and A. Muller, Arch. Pharm., 296, 65 (1963).
(^723) Ger. Pat. 134979; Friedlander, 6, 143 (1902); A. Einhorn, Ann. Chem., 343, 207
(1905).
(^724) H. Hellmann, Angew. Chem., 69, 463 (1957).
(^725) C. L. Parris and R. M. Christenson, /. Org. Chem., 25, 1888 (1960).
(^726) C. M. Suter, R. K. Bair, and F. G. Bordwell, /. Org. Chem., 10, 470 (1945).