The scl enable ... command creates a new shell; you've probably ended up with several nested layers of shells if you've been testing this. If you exit, you'll probably see the gcc --version output from the base system. See how deeply-nested you are with something like pstree -s $$.

To run gcc --version with scl, just put the command on the scl line:

 scl enable devtoolset-9 'gcc --version'

Reference: The Red Hat Developer Toolset 9 User Guide (pdf).

What I have so far:

cat Dockerfile

FROM centos:7 AS env

RUN yum update -y
RUN yum install -y centos-release-scl
RUN yum install -y devtoolset-9

RUN echo "source /opt/rh/devtoolset-9/enable" >> /etc/bashrc
SHELL ["/bin/bash", "--login", "-c"]
RUN gcc --version

So you must:

1. Add the source stuff in a bashrc
   note: On Centos it's /etc/bashrc while on ubuntu it's /etc/bash.bashrc

2. Update the docker default shell to be bash AND to "load" the bashrc using --login

Output

docker build .
Sending build context to Docker daemon  4.096kB
Step 1/32 : FROM centos:7 AS env
 ---> 8652b9f0cb4c
Step 2/32 : RUN yum update -y
 ---> Using cache
 ---> a2bb269cd8dc
Step 3/32 : RUN yum install -y centos-release-scl
 ---> Using cache
 ---> 1184e26c71cf
Step 4/32 : RUN yum install -y devtoolset-9
 ---> Using cache
 ---> e678665d2a4e
Step 5/32 : RUN echo "source /opt/rh/devtoolset-9/enable" >> /etc/bashrc
 ---> Using cache
 ---> fe1745d4ca87
Step 6/32 : SHELL ["/bin/bash", "--login", "-c"]
 ---> Running in 2dd7955f4487
Removing intermediate container 2dd7955f4487
 ---> 3cf4835bf680
Step 7/32 : RUN gcc --version
 ---> Running in b5de3266d607
gcc (GCC) 9.3.1 20200408 (Red Hat 9.3.1-2)
Copyright (C) 2019 Free Software Foundation, Inc.
This is free software; see the source for copying conditions.  There is NO
warranty; not even for MERCHANTABILITY or FITNESS FOR A PARTICULAR PURPOSE.
 ...

What won't work

Test 1

RUN scl enable devtoolset-9 bash
RUN gcc --version | head -1

each RUN is a new shell so the sub-bash is lost on the second line.

Test 2

RUN source /opt/rh/devtoolset-9/enable && gcc --version | head -1
RUN gcc --version | head -1

Here again the source is only for the first RUN shell command but will be lost...

Test 3

This may work but with potential unexpected behaviour

ENV PATH=/opt/rh/devtoolset-9/root/bin:$PATH
RUN gcc --version | head -1

here we only "fix" the PATH variable but if you look at the /opt/rh/devtoolset-9/enable script there is so more to do than only updating the PATH...

I am using CentOS 7.9 and I encountered the same problem after following instructions here to install and run gcc 11. I tried launching different versions of gcc and found only devtoolset-9 works, which corresponds to the file devtoolset-9 in /etc/scl/conf/ folder. So I copied devtoolset-9 to devtoolset-11 in the same folder, and gcc 11 gets working.

You will have to do it the old fashioned way. Get the GCC sources, build it by hand.

Any reason you are averse to doing this? (I can think of a few, but unless you do too, I don't want to add anything that might be confusing).

If you are hesitant to build from sources, I can probably provide some steps.

NOTE: The reason for that is the devtools with 4.9 is currently only available to Red Hat users with a valid license. Wait for a while, and eventually I am sure 4.9 devtools will be made available to CentOS users too like 4.8 is currently.