New Bike 1st and 2nd gear problem

Got a new bike recently and adjusted the gears today for the first time, it was a shop floor bike, not new in box. Ive not had it out a ride yet. Was doing first adjustments today, gears, new grips, saddle adjustments, oiling chain etc.
Anyway its a claud butler cape wrath 04 29er with 27 gears.
So I got the all the gears working fine without rubbing front derailer, but my problem is when I go into 2nd or 1st gear ( biggest front sprocket and 2nd and 1st biggest rear sprocket) the chain comes off the bottom jockey wheel on the rear derailer. Its as if the rear jockey wheel is not adjusting to the chain going from left to right properly, if that makes sense, as in these two particular gears that is when there is the most lateral distance between the rear and front gears
Im not sure what I need to do to fix this issue, can anyone offer some advice.
I can post some pictures if needed, let me know
Anyway its a claud butler cape wrath 04 29er with 27 gears.
So I got the all the gears working fine without rubbing front derailer, but my problem is when I go into 2nd or 1st gear ( biggest front sprocket and 2nd and 1st biggest rear sprocket) the chain comes off the bottom jockey wheel on the rear derailer. Its as if the rear jockey wheel is not adjusting to the chain going from left to right properly, if that makes sense, as in these two particular gears that is when there is the most lateral distance between the rear and front gears
Im not sure what I need to do to fix this issue, can anyone offer some advice.
I can post some pictures if needed, let me know
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Really, I thought all gears should work fine, although I know 1st and 2nd is not gears people would use very much
As a rule of thumb when in the smallest chain ring at the front only use the largest 4 cogs or so at the rear. When in the big chain ring at the front, stick to the smallest 4 or so at the rear. When in the middle chain ring at the front you have more choice at the rear but I'd still avoid using the extremes such as the largest and smallest and stick within 6 or 7 in between.
Basically when you feel yourself shifting to the big cogs on the back, drop down at the front. When shifting to the small cogs on the back shift up at the front. This is good practice and avoids crossing the chain, which will help your chain last longer and make for much better gear selection and easier shifting.
Ideally you want to keep the line your chain follows as straight as possible
I just go by the rule small front not 2 small back, big front not 2 big back. The rest are all good
Usual advice is to follow the parktools guide from start to finish to set up the rear mech properly. If that doesn't work, then come back to ask for more assistance.
2011 Specialized Hardrock Sport Disc (son #4s)
2013 Decathlon Triban 3 (red) (mine)
2019 Hoy Bonaly 26" Disc (son #2s)
2018 Voodoo Bizango (mine)
2018 Voodoo Maji (wife's)
It does go into those gears......
Therefore, something sounds wrong and needs fixing.
I appreciate that I am a technical numpty, but chains coming off jockey wheels is not normal, afaik.
2011 Specialized Hardrock Sport Disc (son #4s)
2013 Decathlon Triban 3 (red) (mine)
2019 Hoy Bonaly 26" Disc (son #2s)
2018 Voodoo Bizango (mine)
2018 Voodoo Maji (wife's)