see http://www.mail-archive.com/openssl-users@openssl.org/msg32453.html

or with exim:
openssl s_client -state -starttls smtp -debug -connect
smtp.privasphere.com:25
CONNECTED(00000003)
read from 080B1378 [080ABFA8] (8192 bytes => 75 (0x4B))
0000 - 32 32 30 20 70 72 69 73-63 69 6c 6c 61 2e 69 6e   220 priscilla.in
0010 - 74 65 72 77 61 79 2e 63-68 20 45 53 4d 54 50 20   terway.ch ESMTP
0020 - 45 78 69 6d 20 34 2e 34-33 20 57 65 64 2c 20 32   Exim 4.43 Wed, 2
0030 - 34 20 4e 6f 76 20 32 30-30 34 20 31 30 3a 35 38   4 Nov 2004 10:58
0040 - 3a 31 32 20 2b 30 31 30-30 0d 0a                  :12 +0100..
write to 080B1378 [BFFFEC50] (10 bytes => 10 (0xA))
0000 - 53 54 41 52 54 54 4c 53-0d 0a                     STARTTLS..
read from 080B1378 [080A9FA0] (8192 bytes => 47 (0x2F))
0000 - 35 30 33 20 53 54 41 52-54 54 4c 53 20 63 6f 6d   503 STARTTLS com
0010 - 6d 61 6e 64 20 75 73 65-64 20 77 68 65 6e 20 6e   mand used when n
0020 - 6f 74 20 61 64 76 65 72-74 69 73 65 64 0d 0a      ot advertised..
SSL_connect:before/connect initialization
write to 080B1378 [080B13C0] (142 bytes => 142 (0x8E))
0000 - 80 8c 01 03 01 00 63 00-00 00 20 00 00 39 00 00   ......c... ..9..
0010 - 38 00 00 35 00 00 16 00-00 13 00 00 0a 07 00 c0   8..5............
0020 - 00 00 33 00 00 32 00 00-2f 03 00 80 00 00 66 00   ..3..2../.....f.
0030 - 00 05 00 00 04 01 00 80-08 00 80 00 00 63 00 00   .............c..
0040 - 62 00 00 61 00 00 15 00-00 12 00 00 09 06 00 40   b..a...........@
0050 - 00 00 65 00 00 64 00 00-60 00 00 14 00 00 11 00   ..e..d..`.......
0060 - 00 08 00 00 06 04 00 80-00 00 03 02 00 80 bc a3   ................
0070 - d3 6f 0c 48 41 97 89 64-32 67 83 af 77 1c 07 ee   .o.HA..d2g..w...
0080 - a2 f5 9f fd e2 e3 57 af-64 8d 15 57 16 38         ......W.d..W.8
SSL_connect:SSLv2/v3 write client hello A
read from 080B1378 [080B6920] (7 bytes => 7 (0x7))
0000 - 35 30 31 20 4e 55 4c                              501 NUL
SSL_connect:error in SSLv2/v3 read server hello A
27159:error:140770FC:SSL routines:SSL23_GET_SERVER_HELLO:unknown
protocol:s23_clnt.c:475:

or also 
openssl s_client -state -starttls smtp -debug -connect mail.swissmail.org:25
CONNECTED(00000003)
read from 080B1378 [080ABFA8] (8192 bytes => 82 (0x52))
0000 - 32 32 30 20 6d 61 69 6c-2e 67 65 6e 65 72 61 6c   220 mail.general
0010 - 6d 61 69 6c 2e 63 6f 6d-20 53 4d 54 50 20 45 6d   mail.com SMTP Em
0020 - 46 6f 53 20 31 2e 30 2c-20 28 43 29 20 31 39 39   FoS 1.0, (C) 199
0030 - 37 20 46 50 57 2f 68 70-77 20 28 68 74 74 70 3a   7 FPW/hpw (http:
0040 - 5c 77 77 77 2e 66 70 77-2e 63 68 29 20 72 65 61   \www.fpw.ch) rea
0050 - 64 79                                             dy
write to 080B1378 [BFFFEC50] (10 bytes => 10 (0xA))
0000 - 53 54 41 52 54 54 4c 53-0d 0a                     STARTTLS..
read from 080B1378 [080A9FA0] (8192 bytes => 2 (0x2))
0000 - 0d 0a                                             ..
SSL_connect:before/connect initialization
write to 080B1378 [080B13C0] (142 bytes => 142 (0x8E))
0000 - 80 8c 01 03 01 00 63 00-00 00 20 00 00 39 00 00   ......c... ..9..
0010 - 38 00 00 35 00 00 16 00-00 13 00 00 0a 07 00 c0   8..5............
0020 - 00 00 33 00 00 32 00 00-2f 03 00 80 00 00 66 00   ..3..2../.....f.
0030 - 00 05 00 00 04 01 00 80-08 00 80 00 00 63 00 00   .............c..
0040 - 62 00 00 61 00 00 15 00-00 12 00 00 09 06 00 40   b..a...........@
0050 - 00 00 65 00 00 64 00 00-60 00 00 14 00 00 11 00   ..e..d..`.......
0060 - 00 08 00 00 06 04 00 80-00 00 03 02 00 80 3a 43   ..............:C
0070 - 98 59 4a 53 dc d0 f0 6f-a3 95 f6 ec 54 23 a1 de   .YJS...o....T#..
0080 - 63 b3 80 e9 b2 15 6e c9-bd 70 7d 27 d6 f2         c.....n..p}'..
SSL_connect:SSLv2/v3 write client hello A
read from 080B1378 [080B6920] (7 bytes => 7 (0x7))
0000 - 35 35 30 20 49 6c 6c                              550 Ill
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