SUNLAMP-IRRADIATED PHASE-TRANSFER CATALYSIS .2. COBALT CARBONYL CATALYZED CARBONYLATION OF BENZYLTRIETHYLAMMONIUM OR ALLYLTRIETHYLAMMONIUM HALIDES UNDER 1 ATM OF CARBON-MONOXIDE
SUNLAMP-IRRADIATED PHASE-TRANSFER CATALYSIS .2. COBALT CARBONYL CATALYZED CARBONYLATION OF BENZYLTRIETHYLAMMONIUM OR ALLYLTRIETHYLAMMONIUM HALIDES UNDER 1 ATM OF CARBON-MONOXIDE
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DOI：
10.1021/jo00159a031
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发表时间：
1983-01-01
影响因子：
3.6
通讯作者：
CAUBERE, P
中科院分区：
文献类型：
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作者：
BRUNET, JJ;SIDOT, C;CAUBERE, P
苯乙酸。2查阅文献表明，苄基三烷基卤化铵的羰基化反应在一定条件下可能发生。因此，Alper等人6已经证明了在PTC条件下由CH 3 I和Co（CO）4-生成的乙酰基四羰基钴对这种苄基卤化铵的化学计量羰基化。这些作者怀疑在这些反应中苄基自由基的干预。[6]这一建议以及我们的观察（见上文）使我们推测，光刺激SrnI条件1，2可能便于进行苄基三烷基卤化铵的催化羰基化。正如我们下面所示，这一预期已得到完全验证，我们在这里提出的第一个催化羰基化苄基-（和烯丙基-）三乙基铵盐。首先，在氯化苄基-三乙基铵上进行的对照实验表明，在没有辐射的情况下，仅形成痕量的苯乙酸（65 ℃，24小时）。该结果证实了文献数据6，但表明在PTC条件下，这种铵盐对Co（CO）4-不是完全惰性的。在任何情况下，光刺激对于进行苄基三乙基卤化铵的羰基化是必不可少的。用一些代表性铵盐获得的结果已在表I中报道。可以看出，这些反应可以在条件A或B（定义见表的脚注a）中的任一种条件下进行，并以75-85%的产率得到相应的酸。正如预期的那样，由于所使用的水解条件，芳环上的腈基被转化为羧基官能团。芳核上带有卤素（Br或Cl）的苄基铵盐被羰基化为二酸，正如我们对（对氯苯基）乙酸羰基化的结果所预期的那样。1
to phenyl acetic acid. 2 Examination of the literature showed that carbonylation of benzyltrialkylammonium halides might take place under certain conditions. Thus, Alper et al. 6 have demonstrated the stoechiometric car-bonylation of such benzylammonium halides by acetylcobalt tetracarbonyl generated from CH3I and Co (CO) 4" under PTC conditions. These authors suspected the in-tervention of benzyl radicals during these reactions. 6 This suggestion as well as our observations (vide supra) led uo to conjecture that the photostimulated SrnI con-ditions1, 2 might be convenient for performing catalytic carbonylation of benzyltrialkylammonium halides. As we show below, this expectation has been completely verified, and we present here the first catalytic carbonylation of benzyl-(and allyl-) triethylammonium salts. First of all, control experiments performed on benzyl-triethylammonium chloride indicated that in the absence of irradiation, only traces of phenylacetic acid were formed (65 C, 24 h). This result confirms literature data6 but shows that such ammonium salts are not completelyinert toward Co (CO) 4-underPTC conditions. In any case, photostimulation appeared essential for performing the carbonylation of benzyltriethylammonium halides. Results obtained with some representative ammonium salts have been reported in Table I. As may be seen, these reactions may be performed in either of the conditions A or B (for definition, see footnote a of the Table) and afford the corresponding acids in 75-85% yield. As expected, nitrile groups on the aromatic ring were transformed into carboxylic functions due to the hydrolyzing conditions used. Benzylammonium salts bearing a halogen (Br or Cl) on the aromatic nucleus were carbonylated to diacids as expected from our result on the carbonylation of (p-chlorophenyl) acetic acid. 1