with stringi:
library(stringi)
df <- read.table(text="ABC|DEF|GHI,1
ABCD|EFG|HIJK,2
ABCDE|FGHI|JKL,3
DEF|GHIJ|KLM,4
GHI|JKLM|NO|PQRS,5
BCDE|FGHI|JKL,6", sep=",", header=FALSE, stringsAsFactors=FALSE)
stri_match_first_regex(df$V1, "(.*?)\\|")[,2]
## [1] "ABC" "ABCD" "ABCDE" "DEF" "GHI" "BCDE"